Synthesis and Characterization of Two Formyl 2-Tetrazenes

• Published in: Chemistry, an Asian journal an Asian journal, 2012-04, Vol.7 (4), p.715-724
• Main Authors: Delalu, Henri, Sabaté, Carlos Miró
• Format: Article
• Language: English
• Subjects: 2-tetrazenes; Chemistry; hydrazines; NMR spectroscopy; Potassium; quantum chemistry; Spectrum analysis; X-ray diffraction
• ISSN: 1861-4728; 1861-471X
• DOI: 10.1002/asia.201100769

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 (1H, 13C, and 15N 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) Å, b=8.714(1) Å, c=13.830(2) Å; α=107.35(1)°, β=90.53(1)°, γ=103.33(1)°; VUC=668.9(2) Å3; Z=4; ρcalc=1.292 cm−3. Compound 3: monoclinic; space group P21/c; a=5.840(2) Å, b=7.414(3) Å, c=8.061(2) Å; β=100.75(3)°; VUC=342(2) Å3; Z=2; ρcalc=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. The synthesis and characterization of two formyl 2‐tetrazenes (see figure) is presented. These compounds may have applications as useful building blocks for the synthesis of materials with interesting energetic properties.