(E)‐1,1,4,4‐Tetramethyl‐2‐tetrazene (TMTZ): A Prospective Alternative to Hydrazines in Rocket Propulsion

Abstract

1,1,4,4-Tetramethyl-2-tetrazene (TMTZ) is considered as a prospective replacement for toxic hydrazines used in liquid rocket propulsion. The heat of formation of TMTZ was computed and measured, giving values well above those of the hydrazines commonly used in propulsion. This led to a predicted maximum I of 337 s for TMTZ/N O mixtures, which is a value comparable to that of monomethylhydrazine. We found that TMTZ has a vapor pressure well below that of liquid hydrazines, and it is far less toxic. Finally, an improved synthesis is proposed, which is compatible with existing industrial production facilities after minor changes. TMTZ is thus an attractive liquid propellant candidate, with a performance comparable to hydrazines but a lower vapor pressure and toxicity.

Site-specific DNA functionalization through the tetrazene-forming reaction in ionic liquids

“…The observation of peaks at 75 (NH) and 300 ppm (N]N) in 15 N NMR in our previous report also support the formation of the disubstituted tetrazene 29 as the tetrasubstituted tetrazene peaks are observed in the slightly more downeld region (NH: 100-180 ppm and N]N: 360-400 ppm). 48,49 With all the mass spectroscopic data in the current and previous report of peptide/protein/DNA substrates that shows the mass shi corresponding to the molecular weight of the azide reagents, the formation of 1,4-disubstituted tetrazene has been supported by our experimental data. Tetrazene-forming reactions of azide species with amine derivatives are also documented and indicated in previous literature.…”

Catalytic Aerobic Oxidation of Hydrazines into 2‐Tetrazenes

“…The milder conditions improved the reactivity of Boc‐protected MMH ( 1 f , entries 10–11) and cyano‐hydrazine 1 i (entries 16 and 17) although the yields remain moderate (but the regular conditions applied to 1 i led to complete degradation). The bis‐Boc‐protected tetrazene 2 f is an interesting structure as it is a protected form of 1,4‐dimethyl 2‐tetrazene, which could be a more effective rocket fuel than spatial hydrazines [12] …”

Energetic Nitrogen‐Rich Polymers with a Tetrazene‐Based Backbone

“…The latter has a high enthalpy of formation. Indeed, trans 1,1,4,4‐tetramethyltetrazene (TMTZ) has a measured Δ H f ° of 214 kJ mol −1 , or 1843 kJ kg −1 [10] . Also, the external nitrogen atoms offer valuable handles for installing substituents, therefore enabling the tuning of mechanical and energetic properties of the polymer (Figure 1).…”

“…Indeed, trans 1,1,4,4-tetramethyltetrazene (TMTZ) has a measured DH f 8 of 214 kJ mol À1 , or 1843 kJ kg À1 . [10] Also, the external nitrogen atoms offer valuable handles for installing substituents, therefore enabling the tuning of mechanical and energetic properties of the polymer (Figure 1). We decided to target polyurethanes (PUs), because PUs offer a wide variety of properties, and therefore are widely employed in industry (construction, furniture, the automotive industry, etc.…”