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Title: Azido and tetrazolo 1,2,4,5-tetrazine N-oxides

Abstract

This paper presents the synthesis and characterization of the oxidation products of 3,6-diazido-1,2,4,5-tetrazine (1) and 6-amino-[1,5-b]tetrazolo-1,2,4,5-tetrazine (2). 3,6-Diazido-1,2,4,5-tetrazine-1,4-dioxide was produced from oxidation with peroxytrifluoroacetic acid, and more effectively using hypofluorous acid, and 2 can be oxidized to two different products, 6-amino-[1,5-b]tetrazolo-1,2,4,5-tetrazine mono-N-oxide and di-N-oxide. These N-oxide compounds display promising performance properties as energetic materials.

Authors:
ORCiD logo [1];  [2];  [3];  [2]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Naval Research Lab., Washington, D.C. (United States)
  3. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1353024
Report Number(s):
LA-UR-16-29593
Journal ID: ISSN 1433-7851
Grant/Contract Number:
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 13; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 1,2,4,5-tetrazine; azides; energetic materials; N-oxides; tetrazole

Citation Formats

Chavez, David E., Parrish, Damon A., Mitchell, Lauren, and Imler, Greg H.. Azido and tetrazolo 1,2,4,5-tetrazine N-oxides. United States: N. p., 2017. Web. doi:10.1002/anie.201612496.
Chavez, David E., Parrish, Damon A., Mitchell, Lauren, & Imler, Greg H.. Azido and tetrazolo 1,2,4,5-tetrazine N-oxides. United States. doi:10.1002/anie.201612496.
Chavez, David E., Parrish, Damon A., Mitchell, Lauren, and Imler, Greg H.. Thu . "Azido and tetrazolo 1,2,4,5-tetrazine N-oxides". United States. doi:10.1002/anie.201612496. https://www.osti.gov/servlets/purl/1353024.
@article{osti_1353024,
title = {Azido and tetrazolo 1,2,4,5-tetrazine N-oxides},
author = {Chavez, David E. and Parrish, Damon A. and Mitchell, Lauren and Imler, Greg H.},
abstractNote = {This paper presents the synthesis and characterization of the oxidation products of 3,6-diazido-1,2,4,5-tetrazine (1) and 6-amino-[1,5-b]tetrazolo-1,2,4,5-tetrazine (2). 3,6-Diazido-1,2,4,5-tetrazine-1,4-dioxide was produced from oxidation with peroxytrifluoroacetic acid, and more effectively using hypofluorous acid, and 2 can be oxidized to two different products, 6-amino-[1,5-b]tetrazolo-1,2,4,5-tetrazine mono-N-oxide and di-N-oxide. These N-oxide compounds display promising performance properties as energetic materials.},
doi = {10.1002/anie.201612496},
journal = {Angewandte Chemie (International Edition)},
number = 13,
volume = 56,
place = {United States},
year = {Thu Feb 23 00:00:00 EST 2017},
month = {Thu Feb 23 00:00:00 EST 2017}
}

Journal Article:
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  • Novel binuclear complexes of heptavalent and pentavalent technetium with the bridging ligand 3,6-bis(2{prime}-pyridyl)-1,2,4,5-tetrazine (bptz) have been prepared and characterized by analysis and optical and vibrational spectroscopy. The heptavalent complexes with the formulation ({mu}-bptz)(TcO{sub 3}X){sub 2} (X = Cl, OCH{sub 3}, OCH{sub 2}CH{sub 3}) were synthesized from pertechnetate and the ligand bptz{center dot}2HCl in the appropriate alcohol (X = OMe, OEt) or from pertechnetate and bptz in ethanolic aqueous HCl (for X = Cl). Binuclear complexes of technetium(V) with the formulation ({mu}-bptz)(TcOCl{sub 2}X){sub 2} (X = OEt, Cl) were prepared in ethanol from TcOCl{sub 4}{sup {minus}} and bptz in the absencemore » (X = OEt) and presence (X = Cl) of ethanolic aqueous HCl. The mononuclear technetium(V) complex (TcO{sub 2}(bptz){sub 2})Cl has also been isolated under certain experimental conditions. Mononuclear complexes of the ligand 4-phenyl-3,6-bis(2{prime}-pyridyl)pyridazine (pppz) with formulae TcO{sub 3}(pppz)Cl and TcO(pppz)Cl{sub 3} were prepared from pertechnetate and TcOCl{sub 4}{sup {minus}}, respectively, with pppz in ethanolic aqueous hydrochloric acid solution.« less
  • Three new coordination polymers, [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl (1), Br (2)) and [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} (3) (bptz=3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) were synthesized. X-ray structural analysis indicated that compounds 1 and 2 are composed of one-dimensional (1D) linear chains while the compound 3 has 1D stair-stepped structure. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that compound 1 and 2 are direct band gap semiconductors; however, compound 3 is an indirect semiconductor. The linear optical properties of the compounds are also calculated by DFT method. According to the DFT calculations, the observed emission bandmore » of the compounds in solid state is due to electron transfer from an excited bptz-π* state (CBs) to the top of VBs. {sup 1}H NMR spectra of the compounds indicate that, in solution phase, the compounds don’t decompose completely. Thermal stability of the compounds is studied using TG, DTA methods. - Graphical abstract: Synthesis, crystal structure and emission spectra of [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl and Br) and [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} are presented. The electronic band structure and linear optical properties of the compounds are calculated by the DFT method. - Highlights: • Three 1D Hg(II) halide coordination polymers with bptz ligand have been prepared. • The structures of the compounds are determined by single crystal XRD. • DFT calculations show that [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl and Br) have a direct band gap. • DFT calculations show that [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} has an indirect band gap. • The compounds show an intraligand electron transfer emission band in solid state.« less
  • The chemical preparation of: (a) 3,6-diamino-1,2,4,5-tetrazine and (b) 3,6-dihydrazino-1,2,4,5-tetrazine is described. The explosive performance of the compounds was calculated with the BKW code. 3 refs., 2 tabs.
  • A photolabile analog of N-1-naphthylphthalamic acid (NPA), 5'-azido-N-1-naphthylphthalamic acid (Az-NPA), has been synthesized and characterized. This potential photoaffinity label for the plasma membrane NPA binding protein competes with (/sup 3/H)NPA for binding sites on Curcurbita pepo L. (zucchini) hypocotyl cell membranes with K/sub 0.5/ = 2.8 x 10/sup -7/ molar. The K/sub 0.5/ for NPA under these conditions is 2 x 10/sup -8/ molar, indicating that the affinity of Az-NPA for the membranes is only 14-fold lower than NPA. While the binding of Az-NPA to NPA binding sites is reversible in the dark, exposure of the Az-NPA treated membranes tomore » light results in a 30% loss in (/sup 3/H)NPA binding ability. Pretreatment of the membranes with NPA protects the membranes against photodestruction of (/sup 3/H)NPA binding sites by Az-NPA supporting the conclusion that Az-NPA destroys these sites by specific covalent attachment.« less
  • It is well recognized that the vitamin D binding protein (DBP) is important for the transport of vitamin D, 25-hydroxyvitamin D (25-OH-D), and its metabolites. In an attempt to better understand the molecular-binding properties of this ubiquitous protein, we designed and synthesized a photoaffinity analogue of 25-OH-D3 and its radiolabeled counterpart. This analogue, 25-hydroxyvitamin D3 3 beta-(N-(4-azido-2-nitrophenyl)glycinate) (25-OH-D3-ANG), was recognized by the rat DBP and was about 10 times less active than 25-OH-D3 in terms of binding. Incubation of (/sup 3/H)25-OH-D3 or (/sup 3/H)25-OH-D3-ANG with rat DBP revealed that both compounds were specifically bound to a protein with a sedimentationmore » coefficient of 4.1 S. Each was displaced with a 500-fold excess of 25-OH-D3. When (/sup 3/H)25-OH-D3-ANG was exposed to UV radiation in the presence of rat DBP followed by the addition of a 500-fold excess of 25-OH-D3, there was no displacement of tritium from the 4.1S peak. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis autoradiographic analysis of (/sup 3/H)25-OH-D3-ANG exposed to UV radiation in the presence of rat DBP followed by the addition of a 500-fold excess of 25-OH-D3 revealed one major band with a molecular weight of 52 000. These data provide strong evidence that (/sup 3/H)25-OH-D3-ANG was covalently linked to the rat DBP. This photoaffinity probe should provide a valuable tool for the analysis of the binding site on this transport protein.« less