Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives Научная публикация

Журнал

Molecules
ISSN: 1420-3049

Вых. Данные

Год: 2020, Том: 25, Номер: 24, Номер статьи : 5836, Страниц : DOI: 10.3390/molecules25245836

Авторы

Larin Alexander A. ¹ , Bystrov Dmitry M. ¹ , Fershtat Leonid L. ¹ , Konnov Alexey A. ¹ , Makhova Nina N. ¹ , Monogarov Konstantin A. ² , Meerov Dmitry B. ² , Melnikov Igor N. ² , Pivkina Alla N. ² , Kiselev Vitaly G. ^2,3,4 , Muravyev Nikita V. ²

Организации

1	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Avenue, 119991 Moscow, Russia.
2	Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 4 Kosygina Str., 119991 Moscow, Russia
3	Institute of Chemical Kinetics and Combustion SB RAS, 3 Institutskaya Str., 630090 Novosibirsk, Russia
4	Novosibirsk State University, 1 Pirogova Str., 630090 Novosibirsk, Russia

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, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-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.

Larin A.A. , Bystrov D.M. , Fershtat L.L. , Konnov A.A. , Makhova N.N. , Monogarov K.A. , Meerov D.B. , Melnikov I.N. , Pivkina A.N. , Kiselev V.G. , Muravyev N.V.
Nitro-, Cyano-, and Methylfuroxans, and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives
Molecules. 2020. V.25. N24. 5836 . DOI: 10.3390/molecules25245836 WOS Scopus OpenAlex

Web of science:	WOS:000603310500001
Scopus:	2-s2.0-85098533776
OpenAlex:	W3112698211

БД	Цитирований
OpenAlex	26
Scopus	24
Web of science	24