An efficient transnitrilation of aryl boronic acids with dimethylmalononitrile (DMMN) is described. This rhodium‐catalyzed electrophilic cyanation presents a novel approach to prepare aryl nitriles by using a carbon‐bound cyanating reagent which undergoes cross‐coupling with the aryl boronic acid. The reaction expands the degree of functional‐group compatibility exhibited by the transnitrilation of aryl Grignard and aryllithium reagents. A variety of aryl boronic acid derivatives and dialkylmalononitriles were amenable to the transnitrilation.
Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression. Graphical Abstract ᅟ.
The 2,4,6‐trinitrotoluene (TNT) replacement, IMX‐101, containing 43.5 % 2,4‐dinitroanisole (DNAN), 19.7 % 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) and 36.8 % nitro‐guanidine (NQ), has been certified for use as an insensitive munition. IMX‐101 has passed standardized performance, stability, and aging tests but in some categories was not necessarily an improvement over TNT or RDX. This study compared the thermal stability of DNAN and another low‐melting nitroarene, 2,4‐dinitrotoulene (DNT). When examined individually, DNAN was more stable; but formulated in IMX‐101 with NTO and NQ, the opposite was true. In two part mixtures, NQ had a similar acceleratory effect on the decomposition of both nitroarenes, while NTO had a greater impact on DNAN than on NTO. Ammonia, a reported decomposition product of both NQ and NTO, also accelerated the decomposition of both DNAN and DNT, with a larger impact on DNAN. The formation of dinitroaniline, potentially due to the interaction between the nitroarenes and ammonia, was detected by LC/MS as a decomposition product when either nitroarene was combined with NTO and/or NQ, indicating that this molecule may play a significant role in the decomposition mechanism. While not advocating the use of DNT in insensitive munitions formulations, this study addresses the importance of chemical compatibility as a criterion for selecting replacement components in formulations.
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