New Energetic Polynitro Cyclic Esters: Ammonium, Hydrazinium, and Hydroxylammonim Salts of Polynitramines

Reaction of 2,2‐dinitro‐1,3‐propanediol (1) with oxalyl dichloride or malonyl dichloride in refluxing ether led to the formation of cyclic dinitro‐containing esters (2, 3) in very good yields. Compounds 2 and 3 were also isolated in similar yields by the treatment of 1 with oxalic acid or malonic ac...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Chemistry : a European journal 2011-10, Vol.17 (42), p.11876-11881
Hauptverfasser: Singh, Rajendra P., Shreeve, Jean'ne M.
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:Reaction of 2,2‐dinitro‐1,3‐propanediol (1) with oxalyl dichloride or malonyl dichloride in refluxing ether led to the formation of cyclic dinitro‐containing esters (2, 3) in very good yields. Compounds 2 and 3 were also isolated in similar yields by the treatment of 1 with oxalic acid or malonic acid in trifluoroacetic anhydride at room temperature. Nitration of 3 with fuming nitric acid resulted in the corresponding trinitro cyclic ester 4 in 70 % isolated yield. Treatment of 1 with a large excess of methanolic ammonia gave impure 2,2‐dinitro‐1,3‐diaminopropane (5). Polynitraamines, 7 and 11, were treated with aqueous ammonia, hydrazine monohydrate or hydroxylamine in methanol at room temperature to obtain their corresponding salts 8–10 and 12–14, respectively, in excellent isolated yields. All new compounds were characterized by IR, NMR spectroscopy (1H, 13C, 15N), DSC, and elemental analysis. Their energetic properties, such as impact sensitivity, detonation velocity, and detonation pressure were also determined and compared with existing energetic compounds, such as PETN (pentaerythritol tetranitrate), RDX (1,3,5‐trinitro‐1,3,5‐triazacyclohexane), and TNT (trinitrotoluene). Taming of the brew: Polynitro cyclic esters exhibit detonation properties similar to TNT, have higher oxygen content, and are much less sensitive to impact. Ammonium, hydrazinium, and hydroxylammonium salts of tetranitramine and trinitramine (see scheme) are markedly less impact sensitive than their molecular precursors.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201101896