The Synthesis and Characterization of a New Furazan Heterocyclic System

David E. Chavez; Damon A. Parrish; Philip Leonard

doi:10.1055/s-0032-1316704

Synlett, Table of Contents

Synlett 2012; 23(14): 2126-2128
DOI: 10.1055/s-0032-1316704

letter

The Synthesis and Characterization of a New Furazan Heterocyclic System

David E. Chavez*

^aLos Alamos National Laboratory, Weapons Experiments Division, Los Alamos, NM 87545, USA, Fax: +1(505)6670500 Email: dechavez@lanl.gov

,

Damon A. Parrish

^bNaval Research Laboratory, Laboratory for the Structure of Matter, Washington, D.C. 20375, USA

,

Philip Leonard

^aLos Alamos National Laboratory, Weapons Experiments Division, Los Alamos, NM 87545, USA, Fax: +1(505)6670500 Email: dechavez@lanl.gov

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Abstract

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Abstract

A new furazan macrocycle, hexakis[1,2,5]oxadiazole[3,4-c:3′,4′-e;3′′,4′′-g:3′′′,4′′′-k:3′′′′,4′′′′-m:3′′′′′,4′′′′′-o][1,2,9,10]- tetraazacyclohexadecine was synthesized by oxidation of diamino trifurazan with trichloroisocyanuric acid. A macrocyclic product is formed under the reaction conditions. The product displays interesting structural properties within the trifurazan segments of the molecule, where the central rings are rotated nearly 90° out of plane from the outer rings. The macrocycle has also been shown to be a sensitive explosive with sensitivity and power similar to the explosive pentaerythritol tetranitrate (PETN). The chemical and explosive properties of this new macrocycle are described in this letter.

Key words

furazan - heterocycle - macrocycle - explosive - azo

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References

References and Notes

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8 Macrocycle 3 To a slurry of diamino trifurazan (1, 2.36 g, 10 mmol) in MeCN (100 mL) was added portionwise trichloroiso-cyanuric acid (4.18 g, 18 mmol). After the addition was complete, the reaction was allowed to stir for 2 h at 25 °C. The solid was filtered and washed with a minimal amount of MeCN. The filtrate was concentrated and purified by column chromatography (CH₂Cl₂) to give 1.74 g (75%) of the desired product; mp 122 °C (dec.). IR (KBr): ν = 1734, 1618, 1559, 1479, 1427, 1395, 1364, 1134, 1051, 1029, 1007, 1002, 988, 910cm^–1. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 133.78, 143.90, 161.41. Anal. Calcd for C₃H₄N₈O₄: C, 31.05; N, 48.27. Found: C, 31.02; N, 48.28. MS (EI): m/z = 232 amu. Macrocycle 4 To a slurry of 3,4-bisamino furazanyl furoxan (1, 2.52 g, 10 mmol) in MeCN (100 mL) was added portionwise trichloroisocyanuric acid (4.18 g, 18 mmol). After the addition was complete, the reaction was allowed to stir for 2 h at 25 °C. The solid was filtered and washed with a minimal amount of MeCN. The filtrate is concentrated and purified by column chromatography (CH₂Cl₂) to give 1.49 g (60%) of the desired product; mp 111 °C (dec.). IR (KBr): ν = 1649, 1605, 1578, 1551, 1513, 1424, 1126, 1046, 1029, 1000, 968, 891cm^–1. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 104.6, 132.43, 134.533, 144.04, 161.12, 161.23. Anal. Calcd for C₁₂N₁₆O₈: C, 29.04; N, 45.16. Found: C, 29.06 N, 45.13. MS (EI): m/z = 248 amu.
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