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Keywords:

  • Nitroso compounds;
  • Alkali metals;
  • NMR spectroscopy;
  • Energetic materials

Abstract

Sodium and potassium methyl(nitroso)amide (M[CH3N2O], M = Na (1), K (2)) were prepared by the reaction of monomethylhydrazine with iso-pentyl nitrite or n-butyl nitrite and a suitable metal ethoxide (M[CH3CH2O], M = Na, K) in an ethanol-ether mixture. The reaction of monomethylhydrazine with a small excess of iso-pentyl nitrite or n-butyl nitrite and in the absence of a metal ethoxide led to the formation of N-nitroso-N-methylhydrazine (CH3(NO)N–NH2, (3)). Alternatively, compound 3 was prepared by the amination reaction of 1 or 2 using the sodium salt of HOSA in ethanol solution. Compounds 1–3 were characterized using elemental analysis, differential scanning calorimetry, mass spectrometry, vibrational (infrared and Raman) and UV spectroscopy and multinuclear (1H, 13C and 15N) NMR spectroscopy. For compounds 1–3, several physical and chemical properties of interest and sensitivity data were measured and for compound 3 thermodynamic and explosive properties are also given. Additionally, the solid-state structure of compound 3 was determined by single-crystal X-ray analysis and the structures of the cis- and trans-[CH3N2O] anions and that of 3 were optimized using DFT calculations and used to calculate the NBO charges.