Synthesis of Nitro- and Acetyl Derivatives of 3,7,10-Trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane

Vera S Glukhacheva; Sergey G Il'yasov; Elena O Shestakova; Egor E Zhukov; Dmitri S Il'yasov; Anastasia A Minakova; Ilia V Eltsov; Andrey A Nefedov; Alexander M Genaev

doi:10.3390/ma15238320

Synthesis of Nitro- and Acetyl Derivatives of 3,7,10-Trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane

Materials (Basel). 2022 Nov 23;15(23):8320. doi: 10.3390/ma15238320.

Authors

Vera S Glukhacheva¹, Sergey G Il'yasov¹, Elena O Shestakova¹, Egor E Zhukov¹, Dmitri S Il'yasov¹, Anastasia A Minakova¹, Ilia V Eltsov², Andrey A Nefedov^{2

3}, Alexander M Genaev³

Affiliations

¹ Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences (IPCET SB RAS), Biysk 659322, Russia.
² Department of Organic Chemistry, Faculty of Natural Sciences, Novosibirsk State University, Novosibirsk 630090, Russia.
³ Department of Physical Organic Chemistry (OPOC), Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences (NIOCh SB RAS), Novosibirsk 630090, Russia.

Abstract

Here, we report the study results of the nitration of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane (THAP) by different nitrating agents such as nitric acid, mixed nitric/sulfuric acids, nitric anhydride, and mixed concentrated nitric acid/acetic anhydride to furnish 3,7,10-trioxo-2-nitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane and 3,7,10-trioxo-2,8-dinitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane, whereas a lactam-lactim rearrangement was found to take place upon vigorous cooling to give 10-hydroxy-2,4,6,8,9,11-hexaazatricyclo[3.3.3.01,5]undec-9-ene-3,7-dione. The two competing reactions, lactam-lactim rearrangement, and nitration were found to take place. The acylation of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane was examined and the formation conditions of 2,6-di- and 2,6,9-triacetyl-substituted and 3,7,10-trioxo-2,4,6,8,9,11-hexaacetyl-2,4,6,8,9,11-hexaaza[3.3.3]propellane were established. The acetyl derivatives were found to be instable in an acidic medium and to undergo deacylation. The obtained findings correlate well with the quantum-chemical calculations.

Keywords: acetylation; nitration; propellane; quantum-chemical predictions.

Grants and funding

The work was performed under the auspices of the Ministry of Science and Higher Education of the Russian Federation (project No. 121061500029-7) using instruments provided by the Biysk Regional Center for Shared Use of Scientific Equipment of the SB RAS (IPCET SB RAS, Biysk).