Investigation of an N‐Butyl‐N‐(2‐Nitroxyethyl)Nitramine (BuNENA) Process: Identification of Process Intermediates, By‐Products and Reaction Pathways

Abstract

A process for N‐butyl‐N‐(2‐nitroxyethyl)nitramine (BuNENA) was investigated: Step 1 involves N‐butyl‐ethanolamine addition to 98% HNO3 to form a salt mixture; Step 2 is addition of acetic anhydride/acetyl chloride catalyst to the salt mixture. A number of potential intermediates, by‐products, and decomposition products from this process were identified/synthesized for use as analytical standards. BuNENA process reaction pathways/mechanisms were elucidated, including the nature of the amine salt solution formed in Step 1. In addition, potential pathways that could account for by‐product formation were elaborated. A study of the consumption of acetyl nitrate in Step 2 was undertaken to prevent its build‐up.

A study on the aliphatic energetic plasticizers containing nitrate ester and nitramine

“…10 were assigned to the nitrate ester amide (Ethyl-NH(C5 5O)-(CH 2 ) 4 -ONO 2 ), whose amine group (-NH(C5 5O)-) is not converted into nitramine (-N(NO 2 )-). However, since the nitrate ester amide 3 with the free amine group was found to be very reactive and unstable itself, as shown in Scheme 4, it can be transformed into some compounds, 4 (product of intramolecular reaction between two molecule of free amine 3) and 5 that cause problems with stability [15]. Therefore, it was realized that the yellow of ENHBAN turned into pale brown slowly during storage, indicating the poor stability of ENHBAN.…”

N-Nitropyridinium Nitrate: An Efficient Nitrating Agent for the Synthesis of 2-[Butyl(nitro)amino]ethyl Nitrate (n-BuNENA)

“…The substance can be absorbed into the body by inhalation of its vapour and by ingestion. However, the present methods suffer from further disadvantages, such as the use of corrosive and dangerous reagents, harsh reaction conditions and the reaction has been performed in a two step process that is not appropriate from both economic and environmental points of view [17]. N-Nitropyridinium nitrate is one of the good nitrating agents, and has been reported in the literature for various nitration reactions [18,19].…”

Thionyl Nitrate as Nitrating Agent for the Synthesis of 2‐[Butyl(nitro)amino]ethyl Nitrate (n‐BuNENA)

“…Several methods for the synthesis of n-BuNENA have been developed to date. Different nitrating agents were used for the nitration of N-butyl ethanolamine and the synthesis of n-BuNENA [14][15][16][17].T hionyl nitrate turned out to be ag ood nitrating agent because during nitration it produces SO 2 as ab y-productt hat leads to shift the reaction to left and finally to ah igher yield according to the Le Chatelier principle [18].T he reagents could be prepared and easily used. This reagent has been prepared by reaction of thionyl chloride and silver nitrateaccording to the literature [17].A ccordingly andi nc ontinuation of studieso nh igh energy compounds [19],h erein the synthesis of n-BuNENA by nitration of N-butylethanolamine with thionyl nitrate was studied.…”