Flow electrochemistry to access and functionalise n-nitramines

Ali, Rojan 2025. Flow electrochemistry to access and functionalise n-nitramines. PhD Thesis, Cardiff University. Item availability restricted.

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Abstract

Energetic materials (EMs) are compounds with a large amount of chemical energy stored, which can be released upon stimulation. EMs have a plethora of civilian and military applications, hence, there is a high demand for such compounds. However, the conventional synthesis of EMs requires hazardous reagents and harsh reaction conditions and, therefore, is environmentally polluting. Over the past decades, a growing interest and increased industrial demand for the development of sustainable synthetic processes have led to organic electrochemistry being used as a promising alternative to activate small organic molecules efficiently and ecologically. The progression towards flow electrochemistry allows for the development of sustainable and easily scalable processes, in line with industrial demand. Herein, we present a two-step electrochemical flow procedure to access N-nitramines, important structural motifs found in numerous energetic materials. First, the N-nitrosation of secondary aliphatic amines using cheap and easy-to-handle sodium nitrite as the nitrosating reagent is presented. Then, the formation of the N-nitro group is achieved via the oxidation of the N-nitroso group using superoxide radical anions as a green oxidant, generated electrochemically from molecular oxygen. Lastly, the electrochemical flow α-C(sp3)–H functionalisation of nitramines proceeding via a Shono-type reaction mechanism has been performed to afford nitramines with additional energetic groups, with the potential to discover novel bifunctional energetic materials.

Item Type:	Thesis (PhD)
Date Type:	Completion
Status:	Unpublished
Schools:	Schools > Chemistry
Date of First Compliant Deposit:	27 March 2026
Last Modified:	27 Mar 2026 10:28
URI:	https://orca.cardiff.ac.uk/id/eprint/186045

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