Search

Amination of 1,1-dimethylhydrazine with NH2 Cl or hydroxylamine-O-sulfonic acid yields 2,2-dimethyltriazanium (DMTZ) chloride (3) and sulphate (4), respectively. The DMTZ cation was paired with the nitrogen-rich anions 5-aminotetrazolate (5), 5-nitrotetrazolate (6), 5,5'-azobistetrazolate (7), and azide (8), yielding a new family of energetic salts. The synthesis was carried out by metathesis reactions of salts 3 or 4 and a suitable silver or barium salt. To minimize the risks involved when using heavy metal salts, we used electrodialysis for the synthesis of azide 8, which avoids the use of highly sensitive species. The DMTZ derivatives were characterized by IR and multinuclear NMR spectroscopy, elemental analysis, and X-ray diffraction. Thermal stabilities were measured using DSC analysis and their sensitivities towards classical stimuli were determined using standard tests. Lastly, the relationship between hydrogen bonding in the solid state and sensitivity is discussed.

We synthesized nitrosamines (R2N-NO) with R = iPr (1), nPr (2), nBu (3), and hydroxyethyl (4) from the amine using sodium nitrite/p-toluenesulfonic acid in CH2Cl2. The rate of formation of 1-4 increases in the direction iPr

The synthesis of two formyl 2-tetrazenes, namely, (E)-1-formyl-1,4,4-trimethyl-2-tetrazene (2) and (E)-1,4-diformyl-1,4-dimethyl-2-tetrazene (3), by oxidation of (E)-1,1,4,4-tetramethyl-2-tetrazene (1) using potassium permanganate in acetone solution is presented. Compound 3 was also synthesized in an improved yield from the oxidation of 1-formyl-1-methylhydrazine (4a) using potassium permanganate in acetone. Both compounds 2 and 3 were characterized by analytical (elemental analysis, GC-MS) and spectroscopic methods ((1)H, (13)C, and (15)N NMR spectroscopy, and IR and Raman spectroscopy). In addition, the solid-state structures of the compounds were confirmed by low-temperature X-ray analysis. (Compound 2: triclinic; space group P-1; a=5.997(1) A, b=8.714(1) A, c=13.830(2) A; α=107.35(1)°, β=90.53(1)°, γ=103.33(1)°; V(UC) =668.9(2) A(3); Z=4; ρ(calc)=1.292 cm(-3). Compound 3: monoclinic; space group P2(1)/c; a=5.840(2) A, b=7.414(3) A, c=8.061(2) A; β=100.75(3)°; V(UC)=342(2) A(3); Z=2; ρ(calc)=1.396 g cm(-3).) The vibrational frequencies of compounds 2 and 3 were calculated using the B3LYP method with a 6-311+G(d,p) basis set. We also computed the natural bond orbital (NBO) charges using the rMP2/aug-cc-pVDZ method and the heats of formation were determined on the basis of their electronic energies. Furthermore, the thermal stabilities of these compounds, as well as their sensitivity towards classical stimuli, were also assessed by differential scanning calorimetry and standard BAM tests, respectively. Lastly, the attempted synthesis of (E)-1,2,3,4-tetraformyl-2-tetrazene (6) is also discussed.