Synthesis and Electrochemical Behavior of Electron-Rich s-Tetrazine and Triazolo-tetrazine Nitrate Esters
Abstract
Abstract We have prepared energetic nitrate ester derivatives of 1,2,4,5‐tetrazine and 1,2,4‐triazolo[4,3‐ b ]‐[1,2,4,5]‐tetrazine ring systems as model compounds to study the electrochemical behavior of tetrazines in the presence of explosive groups. The model compounds showed lower thermal stabilities relative to PETN (pentaerythritol tetranitrate), but slightly improved mechanical sensitivities. The presence of electron‐rich amine donors leads to a cathodic shift of the tetrazine redox potentials relative to those of previously reported tetrazine explosives. At these potentials, electron‐rich tetrazines with either covalently bound or co‐dissolved nitrate ester groups are irreversibly reduced. Effectively, changes in the electronic structure of tetrazines affect their electrochemical response to the presence of nitrate ester groups. Thus, it may be possible to develop tetrazine‐based electrochemical sensors for the detection of specific explosives and electrocatalysts for their disposal.
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1499341
- Alternate Identifier(s):
- OSTI ID: 1401857
- Report Number(s):
- LA-UR-16-23402
Journal ID: ISSN 0947-6539
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 22; Journal Issue: 30; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Myers, Thomas Winfield, Snyder, Christopher J., Chavez, David E., Scharff, Robert Jason, and Veauthier, Jacqueline Marie. Synthesis and Electrochemical Behavior of Electron-Rich s-Tetrazine and Triazolo-tetrazine Nitrate Esters. United States: N. p., 2016.
Web. doi:10.1002/chem.201601422.
Myers, Thomas Winfield, Snyder, Christopher J., Chavez, David E., Scharff, Robert Jason, & Veauthier, Jacqueline Marie. Synthesis and Electrochemical Behavior of Electron-Rich s-Tetrazine and Triazolo-tetrazine Nitrate Esters. United States. https://doi.org/10.1002/chem.201601422
Myers, Thomas Winfield, Snyder, Christopher J., Chavez, David E., Scharff, Robert Jason, and Veauthier, Jacqueline Marie. Mon .
"Synthesis and Electrochemical Behavior of Electron-Rich s-Tetrazine and Triazolo-tetrazine Nitrate Esters". United States. https://doi.org/10.1002/chem.201601422. https://www.osti.gov/servlets/purl/1499341.
@article{osti_1499341,
title = {Synthesis and Electrochemical Behavior of Electron-Rich s-Tetrazine and Triazolo-tetrazine Nitrate Esters},
author = {Myers, Thomas Winfield and Snyder, Christopher J. and Chavez, David E. and Scharff, Robert Jason and Veauthier, Jacqueline Marie},
abstractNote = {Abstract We have prepared energetic nitrate ester derivatives of 1,2,4,5‐tetrazine and 1,2,4‐triazolo[4,3‐ b ]‐[1,2,4,5]‐tetrazine ring systems as model compounds to study the electrochemical behavior of tetrazines in the presence of explosive groups. The model compounds showed lower thermal stabilities relative to PETN (pentaerythritol tetranitrate), but slightly improved mechanical sensitivities. The presence of electron‐rich amine donors leads to a cathodic shift of the tetrazine redox potentials relative to those of previously reported tetrazine explosives. At these potentials, electron‐rich tetrazines with either covalently bound or co‐dissolved nitrate ester groups are irreversibly reduced. Effectively, changes in the electronic structure of tetrazines affect their electrochemical response to the presence of nitrate ester groups. Thus, it may be possible to develop tetrazine‐based electrochemical sensors for the detection of specific explosives and electrocatalysts for their disposal.},
doi = {10.1002/chem.201601422},
journal = {Chemistry - A European Journal},
number = 30,
volume = 22,
place = {United States},
year = {Mon Jun 27 00:00:00 EDT 2016},
month = {Mon Jun 27 00:00:00 EDT 2016}
}
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Cited by: 14 works
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Figures / Tables:
Scheme 1: Attempted reactions of TrisTN with tetrazine electrophiles.
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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.