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Amination of nitroazoles--a comparative study of structural and energetic properties.

ABSTRACT: In this work, 3-nitro-1H-1,2,4-triazole (1) and 3,5-dinitro-1H-pyrazole (2) were C-aminated and N-aminated using different amination agents, yielding their respective C-amino and N-amino products. All compounds were fully characterized by NMR (1H, 13C, 15N), IR spectroscopy, differential scanning calorimetry (DSC). X-ray crystallographic measurements were performed and delivered insight into structural characteristics as well as inter- and intramolecular interactions of the products. Their impact sensitivities were measured by using standard BAM fallhammer techniques and their explosive performances were computed using the EXPLO 5.05 program. A comparative study on the influence of those different amino substituents on the structural and energetic properties (such as density, stability, heat of formation, detonation performance) is presented. The results showed that the incorporation of an N-amino group into a nitroazole ring can improve nitrogen content, heat of formation and impact sensitivity, while the introduction of a C-amino group can enhance density, detonation velocity and pressure. The potential of N-amino and C-amino moieties for the design of next generation energetic materials is explored.

SUBMITTER: Zhao X

PROVIDER: S-EPMC6272014 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

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Amination of nitroazoles--a comparative study of structural and energetic properties.

Zhao Xiuxiu X Qi Cai C Zhang Lubo L Wang Yuan Y Li Shenghua S Zhao Fengqi F Pang Siping S

Molecules (Basel, Switzerland) 20140114 1

In this work, 3-nitro-1H-1,2,4-triazole (1) and 3,5-dinitro-1H-pyrazole (2) were C-aminated and N-aminated using different amination agents, yielding their respective C-amino and N-amino products. All compounds were fully characterized by NMR (1H, 13C, 15N), IR spectroscopy, differential scanning calorimetry (DSC). X-ray crystallographic measurements were performed and delivered insight into structural characteristics as well as inter- and intramolecular interactions of the products. Their impac ...[more]

PMID: 24424403

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Project description:Density functional theory (DFT and time-dependent-DFT (TD-DFT) were employed to investigate the vibroelectronic structural properties of porphyrin and some derivatives: unsubstituted porphyrin (TPyr), meso-tetraphenylporphyrin (TPP), meso-tetrakis(p-sulfonatophenyl)porphyrin (TSPP), protonated-TPyr (H2TPyr), deuterated-H2TPyr (D4TPyr), protonated-TPP (H2TPP) and deuterated-H2TPP (D4TPP), protonated TSPP (H2TSPP), deuterated-H2TSPP (D4TSPP), dicationic TSPP (H6TSPP) and deuterated-H6TSPP (D8TSPP). The possible internal conversion (IC) and intersystem crossing (ISC) processes of these compounds were investigated. Finally, the relaxed ground state potential energy surface (PES) (S0), and singlet (Sn, n = 1-24) and triplet (Tn) excited state PESs of the TSPP molecule were calculated as function of the dihedral angle (C?-Cm-C?-C(ph)) rotation. The results of the calculations indicated that while the meso-substitutions caused a significant shift in frequencies when the meso-carbons within the parent-porphine (or TPyr) are involved in the vibrational motion of molecules; the protonation of the N atoms at the porphine/porphyrin core causes a significant blue shift when the H on the N atoms within the pyrroline are dominantly involved in the vibrational motions. The deuteration of N atoms not only caused a red-shift in the frequencies of the corresponding peaks below 1600 cm(-1), but also produced new vibrational modes of frequencies in the 2565-2595 cm(-1) range caused by the N-D bond stretching. Similarly, the deuteration of O atoms within the sulfonato groups (-SO3(-)) exhibited a new peak at around 2642 cm(-1) due to O-D bond stretching. The measured Raman spectrum of the H2TSPP is assigned based on the predicted Raman spectra of the compounds studied here and measured Raman spectrum of the TPP (from our previous work). The IR spectrum is assigned based on our calculations and measured IR spectra obtained from the literature. The results of the TD-DFT calculations did not only indicate that the meso-substitution and protonation of the porphyrin bring about a significant read shift in the electronic transitions; but also provided a strong evidence for the IC from the Soret band to Q-bands beside possibility of the ISC process; its existence depend on the other excited state process such as much faster vibrational relaxation; the IC and etc. The ground state PES curve (S0) of the ionic TSPP exhibited two minima at the dihedral angle (C?-Cm-C?-C) of about 66° (corresponds to the lowest ground state) and 110° (corresponds to next energetically stable state or the local minima). The energy deference between these two minima is 0.0132 eV (or 106 cm(-1)) and the highest potential energy barrier when undergoing from the lowest ground state to this local state is only 0.0219 eV (177 cm(-1); which is compatible with the thermal energy (kT) at 298 K is 207.2 cm(-1).

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Amination of nitroazoles--a comparative study of structural and energetic properties.

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Amination of nitroazoles--a comparative study of structural and energetic properties.

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