An Improved Process Towards Hexahydro‐1,3,5‐trinitroso‐1,3,5‐triazine (TNX)

Abstract

Hexahydro‐1,3,5‐trinitroso‐1,3,5‐triazine (TNX) is mostly known as a by‐product in the environmental decomposition of RDX. The original chemistry to TNX was never optimized and thus resulted in low yields due to competitive degradation of the starting material. Enabled conditions to TNX were developed by optimizing pH effects and mitigating foaming by reactor geometry and stirring. The conditions presented herein allow for the inexpensive and simple production of multi‐gram quantities of TNX. The isolated TNX obtained by our new method was characterized by 1H NMR, 13C NMR, DSC, and X‐ray crystallography. A preliminary evaluation of the sensitivity of TNX towards impact and friction is also presented.

Experimental Vapor Pressures of Hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and Hexahydro‐1,3,5‐trinitroso‐1,3,5‐triazine (TNX)

“…TNX was prepared according to the procedure described in the work of Rothstein et al . . The purity of the compounds used in this study (Figure ) was tested by EA, 1 H‐, 13 C‐, 14 N‐NMR, and HPLC‐DAD techniques.…”

A comprehensive study on the thermal properties and chemical characterization of 1,3,5‐trinitroso‐1,3,5‐triazine (R‐Salt)

“…R-Salt was synthesized in small batches based on previously described methods [11][12][13]29]. The synthesis route for R-Salt (Scheme 1) involves mixing hexamine with nitrous acid (HNO 2 ).…”

“…Nitrous acid is an unstable weak acid, and it must be generated in situ by mixing a nitrite salt with a mineral acid catalyst. Within literature, hydrochloric acid is frequently employed [7,11,12]; sulfuric acid and acetic acid have also been used [13]. While the acid catalyst is necessary to produce nitrous acid, the pH of the solution determines which product will form.…”

“…Proton 1 H and carbon 13 C nuclear magnetic resonance (NMR) spectra were recorded on a Bruker Advance 400 MHz spectrometer located at Stockton University, Galloway, NJ 08205, and 1 H NMR spectra were recorded on a Nanalysis NMReady Benchtop 60PRO 60 MHz spectrometer at ambient temperature and pressure. Samples were prepared at approximately 0.1 molar concentration in dimethyl sulfoxide-d 6 (DMSO-d 6 ) with 0.03 % percent tetramethylsilane (TMS) as the internal chemical shift reference.…”

“…The importance of maintaining a particular pH in the synthesis of R-Salt was later reported in the 1950's [11,12]. Efforts exist to continue development and improve manufacturing of R-Salt due to persistently low yields [13]. Because the production of R-Salt doesn't require a strong acid, it was once considered for large scale manufacturing during World War II [7].…”