A facile method to construct a 2,4,9-triazaadamantane skeleton and synthesize nitramine derivatives

Abstract

An unusual protocol for a “one-pot” three-step reaction to build a 2,4,9-triazaadamantane skeleton from triallylcarbinol was developed.

Pentacycloundecane (PCUD)‐Based Cage Frameworks as Potential Energetic Materials: Syntheses and Characterization

“…Finally, the cycloadduct 23 smoothly underwent intramolecular photocycloaddition reaction [2 + 2 cycloaddition] in dry EtOAc upon exposure to UV light (125 W) in pyrex immersion well for 1 h to yield the target product cage bistriazole 9 in 86% yield. The spectral data ( 1 H NMR, 13 C NMR, DEPT-135, and APT) of target product 9 obtained via this path (Scheme 2) were identical to the same compound 9 prepared by earlier method as shown in Scheme 1.…”

“…Finally, to assemble our target molecule 9, the cage bisazide 21 was subjected to click reaction with phenylacetylene in the presence of copper sulfate and sodium ascorbate in tertbutanol/water suspension, thus furnishing the cage bis-triazole 9 in 67% yield. The structures of the bis-triazole 9 and bis-azide 21 were fully supported by 1 H NMR, 13 C NMR, DEPT-135, APT and further confirmed by HRMS (Scheme 1). Further, the structures of these cage diones 9 and 21 were firmly established by X-ray studies (Figure 3).…”

“…Benzene and DCM were distilled by calcium hydride (CaH 2 ) and EtOAc was dried with anhydrous K 2 CO 3 . 1 H, 13 C and DEPT 135 NMR data have been recorded on 400 and 500 MHz spectrometers (Bruker). Mass spectra (HRMS) have been recorded under positive ion electrospray ionization (ESI, Q-TOF) mode.…”

2,4,4,8,8‐Pentanitro‐2‐Azaadamantane: A High‐Density Energetic Compound

“…In the late 1990s, 2,4,10‐trinitro‐2,4,10‐triazaadamantane was prepared by Nielsen and co‐workers . Recently, our group reported the synthesis of 2,4,9‐trinitro‐2,4,9‐triazaadamantane‐7‐yl nitrate, which shows highly thermostable and performance . This communication outlines the synthesis of 2,4,4,8,8‐pentanitro‐2‐azaadamantane ( 1 ), a novel high‐performance energetic material of the polynitroazaadamantane family.…”

Synthesis and Properties of Tetranitro‐Substituted Adamantane Derivatives

“…Their calculated densities, sensitivities, and detonation properties are similar to those obtained for standard high explosives like RDX (hexogen), HMX (octogen), TNT (trinitrotoluene), and PETN (pentaerithrityltetranitrate) . Most recently the novel high‐energy‐density compound 2,4,9‐trinitro‐2,4,9‐triazaadamantane‐7‐yl nitrate was prepared and characterized, featuring high thermal stability and high density . According to the calculated energetic properties, some of the polynitro derivatives of the simple adamantane, such as 1,3,5,7‐adamantane tetranitrate and 1,3,5,7‐tetrakis(trinitroxymethyl)adamantane, might even have better performance values than TNT .…”