Synthesis, Characterization, and Energetic Properties of Nitroso Compounds

Sodium and potassium methyl(nitroso)amide ( M [CH 3 N 2 O], 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 [CH 3 CH 2 O], 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 (CH 3 (NO)N–NH 2 , ( 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 ( 1 H, 13 C and 15 N) 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 ‐[CH 3 N 2 O] – anions and that of 3 were optimized using DFT calculations and used to calculate the NBO charges.