TY - JOUR

T1 - Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives

T2 - From Green Primary to Melt-Cast Explosives

AU - Larin, Alexander A.

AU - Bystrov, Dmitry M.

AU - Fershtat, Leonid L.

AU - Konnov, Alexey A.

AU - Makhova, Nina N.

AU - Monogarov, Konstantin A.

AU - Meerov, Dmitry B.

AU - Melnikov, Igor N.

AU - Pivkina, Alla N.

AU - Kiselev, Vitaly G.

AU - Muravyev, Nikita V.

N1 - Publisher Copyright: © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2020/12/10

Y1 - 2020/12/10

N2 - In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 ◦C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,40-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,30-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.

AB - In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 ◦C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,40-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,30-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.

KW - 1,2,5-oxadiazole-2-oxide

KW - detonation performance

KW - energetic materials

KW - furoxan

KW - mechanical sensitivity

KW - melt-cast explosives

KW - quantum chemistry

KW - regioisomerism

KW - thermochemistry

KW - THERMOLYSIS

KW - THERMODYNAMIC PROPERTIES

KW - 5-oxadiazole-2-oxide

KW - PERFORMANCE

KW - 1

KW - FUROXAN

KW - 2

KW - ENTHALPY

KW - DETONATION

KW - COMPUTATION

KW - NITRATION

UR - http://www.scopus.com/inward/record.url?scp=85098533776&partnerID=8YFLogxK

U2 - 10.3390/molecules25245836

DO - 10.3390/molecules25245836

M3 - Article

C2 - 33322001

AN - SCOPUS:85098533776

VL - 25

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 24

M1 - 5836

ER -