An Efficient Route to 1,3,5-Triazido-2,4,6-tricyanobenzene

Abstract

An efficient synthetic route starting from 1,3,5-trimethylbenzene is described for binary 1,3,5-triazido-2,4,6-tricyanobenzene. Besides 1,3,5-triazido-2,4,6-tricyanobenzene, all intermediates have been isolated and fully characterized.

Six-Membered Aromatic Polyazides: Synthesis and Application

“…The nucleophilic substitution reactions were also used to prepare triazidobenzenes 88 , 90 and 92a – c from the corresponding halides (Scheme 24) [127,128,129,130]. The azidation of halides 87a , b with sodium azide in boiling acetonitrile gave triazide 88 in high yield [127,128]. Similarly, the azidation of trichloride 89 with trimethylsilylazide in acetonitrile at room temperature afforded triazide 90 in quantitative yield [129].…”

“…Unfortunately, halides 87a , b and 89 are hardly available compounds what seriously limits the use of triazides 88 and 90 in practice. Thus, tribromide 87b is prepared from mesitylene in six steps [128]. Both triazides 88 (m.p.…”

“…113–114 °C) are solids that are almost insensitive toward impact, friction and electrostatic discharge. Triazide 88 has the highest melting point among all six-membered aromatic triazides [128]. Recently, a simple and efficient method of preparation of triazidobenzenes 92a – c from commercially available trifluorides 91a – c has been developed (Scheme 24) [130].…”

“…Recent X-ray diffraction studies have shown that the azido groups of triazides 81 and 88 are rotated out of the C 6 plane in order to reduce steric repulsion [124,128]. Due to this effect, all three azido groups of 81 and 88 are structurally nonequivalent and slightly differ in the C–Nα, Nα–Nβ and Nβ–Nγ bond distances and the C–Nα–Nβ and Nα–Nβ–Nγ angles.…”

Redox Reactions Between Guanidine Electron Donors and Silver Dicyanamide: Synthesis of C,N Material Precursors and Coordination Polymers

“…These compounds exhibit a relatively high nitrogen content of 32 wt.‐% (N/C molar ratio of 0.5). Unfortunately, all attempts to synthesize the parent nitrogen‐rich compound tgb (1,2,4,5‐tetraguanidinylbenzene) with an N/C molar ratio of 1.2 (55 wt.‐% N),14 close to the ideal value of 1.3 for C 3 N 4 , failed (instead undefined polymeric compounds were formed).…”