Michael A. Hiskey

1,2,4,5-TETRAZINE BASED ENERGETIC MATERIALS

Abstract The synthesis and properties of several new energetic 1,2,4,5-tetrazine derivatives are described. These include energetic salts of 3,6-dihydrazino-1,2,4,5-tetrazine and several symmetrically and unsymmetrically substituted tetrazines with energetic substituents, in addition to a new nitro-tetrazine.

4,4′,6,6′-Tetra-Substituted Hydrazo- and Azo-1,3,5-Triazines

The syntheses of 4,4′,6,6′-tetra(amino)- (1), tetra(hydroxylamino)- (2), tetra(hydrazino)- (3), and tetra(azido)hydrazo-1,3,5-triazines (4) are described. Compound (4) was oxidized to 4,4′,6,6′-tetra(azido)azo-1,3,5-triazine (5). The thermal and sensitivity properties of (4) and (5) are reported in addition to all physical properties of new compounds

Synthesis and initial characterization of some energetic salts of 3,3-dinitroazetidine

Abstract Six energetic salts of 3,3-dinitroazetidine (DNAZ) were prepared. Methods of preparation for the nitrate (1), 2,4-dinitroimidazolate (2), 4,4′,5,5′-tetranitro-2,2′-biimidazolate (3), dinitramidate (4), 5-nitro-1,2,4-triazol-3-onate (5), and 3,5-dinitro-1,2,4-triazolate (6) are given. Results from initial characterization, small-scale sensitivity tests, heats of formation, density, and 13C-nmr spectra are also reported. DNAZ-nitrate (1) was easily dehydrated to 1,3,3-trinitroazetidine (TNAZ) (7).

3-Amino-6-nitroamino-tetrazine (ANAT)-based energetic salts

The synthesis and properties of several new high-nitrogen materials with 3-amino-6-nitroamino-tetrazine (ANAT) as the anion are reported; all salts were fully characterized by IR and NMR spectroscopy, and elemental analysis.

Preparation, Characterization, and Properties of 7-Nitrotetrazolo[1,5-f ]furazano[4,5-b]pyridine 1-Oxide

ABSTRACT The synthesis, characterization, and properties of 7-nitro-tetrazolo[1,5-f]furazano[4,5-b]pyridine 1-oxide (NFP) are reported. NFP is prepared by the diazotization of 3,6-di(hydrazino)-3,5-di(nitro)pyridine followed by the extrusion of molecular dinitrogen and ring closure.

Scale-up and waste-minimization of the Los Alamos process for 1,3,3-trinitroazetidine (TNAZ)

Abstract The original synthesis of TNAZ (1,3,3-trinitroazetidine) was developed by T. G. Archibald in 1983 and was scaled up to produce several hundred kg of TNAZ for evaluation by the DoD. Although the synthesis method utilizes inexpensive starting materials, it is a multi-step process that gives less than 20% overall yields and produces significant chemical waste (over 1200 kg kg −1 of TNAZ), including large quantities of halogenated solvents. An alternative synthesis, which gives much higher yields of TNAZ and less waste than obtained from the original process, was developed at the Los Alamos National Laboratory. The technology was transferred to Aerojet, Sacramento, where it was scaled up to production-plant quantities to give TNAZ in 57% overall yield. The new process produced about 10% of the waste produced in the original process without recycle of solvents or reagents. It is estimated that recycle of solvents and reagents will reduce the chemical waste to 15.7 kg kg −1 of TNAZ. Further improvements in waste reduction have been demonstrated that may eventually lead to a process giving little more than 3.7 kg of chemical waste kg −1 of TNAZ in addition to the energy burden encountered with any industrial process.

Giant Momentum Coupling Coefficients from Nanoscale Laser-initiated Exothermic Compounds

*† ‡ § ** †† ‡‡ We report here on results obtained with laser-initiated micro-propellants, such as PVN, PVC, GAP, NC, and mixtures of these. All samples were doped with a laser absorbing component. In some cases, this was carbon nanopearls with 10nm mean diameter, while, in others, it was a carbon-based ink with ∝m-size particles. We also report results of performance tests for absorbers tuned to the 935-nm laser wavelength.

Preparation and Explosive Properties of Tetraamminebis(3,5-Dinitro-1,2,4-Triazolato-N1)Copper(II)

ABSTRACT The synthesis of tetraamminebis(3,5-dinitro-1,2,4-triazolato-N1)copper(II) is reported along with its physical and sensitivity properties as well as crystal structure. In addition, the detonation velocity and CJ pressure have been determined at 0.5 inch diameter.

Improved synthetic routes to polynitroheterocycles

Abstract The preparations of several explosive precursors utilizing oxidative nitration are described. These include 1,3-di-t-butyl-5,5-dinitrohexahydropyrimidine, 3-t-butyl-5,5-dinitrotetrahydro-1,3-oxazine, 2,2-dinitro-1,3-propanediol (ADIOL) and potassium aci-2,2-dinitroethanol. The former pyrimidine and oxazine precursors were nitrolyzed to 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and 3,5,5-trinitrotetrahydro-1,3-oxazine (TriNOx). ADIOL, a widely used reagent in explosives preparation, was prepared by the trans-ketalization of 2,2-dimethyl-5,5-dinitro-1,3-dioxane. The dioxane was prepared in high yield by the oxidative nitration of 5-hydroxymethyl-2,2-dimethyl-5-nitro-1,3-dioxane. The little known explosive, 1,3,3,5,5-pentanitro-piperidine (PNP), has been prepared from potassium aci-2,2,4,4-tetranitrobutanol and t-butylamine hydrochloride. The vacuum thermal stabilities of DNNC, TriNOx and PNP at 100°C are reported.

Preparation and Properties of 2,4,8,10-Tetranitro-5H-Pyrido[3′,2′:4,5][1,2,3] Triazolo[1,2–a]Benzotriazol-6-ium Inner Salt as a Thermally Stable High Explosive

The synthesis and explosive properties of 2,4,8,10-tetranitro-5H-pyrido[3′, 2′:4, 5] [1,2,3] triazolo [1,2-a] benzotriazol-6-ium inner salt (7) are given. This material is a very thermally stable high explosive that has a differential scanning calorimetry (DSC) onset of 365°C with fast decomposition occurring at 375°C. The material is readily prepared in three steps from inexpensive starting materials. The final compound is insensitive to initiation by spark and friction and has a drop height of 59 cm (Type 12, 2.5 kg weight, HMX = 23 cm). In addition, it has a failure diameter of less than 3 mm. A detonation velocity of 7.43 km/s and detonation pressure of 294 kbar were determined on 0.5 inch pellets at a density of 1.78 g/cm3.