Nitrolysis of a Highly Deactivated Amide by Protonitronium. Synthesis and Structure of HNFX¹

Abstract

Efficient N-nitrolysis of highly deactivated 3,3,7,7-tetrakis(difluoramino)octahydro-1,5-bis(4-nitrobenzenesulfonyl)-1,5-diazocine (1) has been achieved by the use of protonitronium reagent formed in the system nitric acid-trifluoromethanesulfonic acid, producing 3,3,7,7-tetrakis(difluoramino)octahydro-1,5-dinitro-1,5-diazocine (HNFX, 2) in 65% yield in a nonoptimized reaction. The crystal structure of the first morphology of HNFX contains cavities in the form of channels through its unit cell; the observed density is 1.807 g.cm(-)(3).

Organic cyclic difluoramino‐nitramines: infrared and Raman spectroscopy of 3,3,7,7‐tetrakis(difluoramino)octahydro 1,5‐dinitro‐1,5‐diazocine (HNFX)

“…symmetry conformer calculated at different levels of theory are given in Table 1 along with X-ray diffraction data of crystalline HNFX. [6] Average absolute deviations of the calculated bond lengths and bond angles from crystallographic measurements range within 0.8-1.6% and 0.9-1.2%, respectively, using the various theoretical treatments. These results suggest the absence of significant molecular distortion induced by the crystal field at ambient conditions, consistent with previous structural studies of organic molecular solids.…”

“…The first high-yield synthesis and structural characterization of the HNFX crystal, with stoichiometry C 6 H 8 F 8 N 8 O 4 , were carried out by Chapman et al [5,6] X-ray crystallographic analysis indicates that HNFX recrystallizes at ambient pressure and temperature from a variety of solvents in the rhombohedral space group R3∼, C3i.2, with nine molecules per unit cell (cf. Fig.…”

“…[6] Although cyclic nitramines incorporating eight-membered rings are notorious for exhibiting polymorphism, [7] no experimental evidence of a new HNFX polymorph has been found so far. [6,8] Vibrational spectroscopy measurements and normal-mode analysis based on high-accuracy ab initio electronic structure calculations provide useful information relevant to intramolecular and intermolecular motion energies, which feeds into some of the theories on shock-induced molecular decomposition mechanisms of energetic materials. [9−12] In this work, we present the first vibrational structure investigation of HNFX -and, more generally, of a gem-bis(difluoramino)-substituted heterocyclic nitramine.…”

Density functional theory study of piperidine and diazocine compounds

“…3,3,7,7-Tetrakis(difluoroamino)octahydro-1,5-dinitro-1,5-diazocine (HNFX), 3,3-dinitro-7,7-bis(difluoroamino)octahydro-1,5-dinitro-1,5-diazocine (TNBDFADZ) and 1,3,3,5,7,7-hexanitro-1,5-diazacyclooctane (HNDZ) are analogue energetic compounds [10][11][12][13]. The ring structures of the title compounds are similar to HMX.…”

Open‐Pore Organic Material for Retaining Radioactive I2 and CH3I

“…[9,10] It was claimed earlier that after removal of solvents the hexagonal inclusion lattice (P6/m) converts into a distorted open-pore form (P2/n). [11] However, it was also observed that crystals of a size larger than about 100 lm converted into the monoclinic form during desolvation.…”