3,3′-二硝基-4,4′-氧化偶氮呋咱(DNOAF)的热分解特性

采用热重实验(TG)、差示扫描量热实验(DSC)和气体(固体)原位反应池/快速扫描傅里叶变换红外光谱(RSFTIR)联用技术,研究了3,3′-二硝基-4,4′-氧化偶氮呋咱(DNOAF)的热分解特性。结果表明:DNOAF的热分解特性对压强敏感,随着压强的升高,DNOAF的热分解放热峰温呈降低趋势。其热分解气体中具有红外活性的有CO2,N2O,NO,NO2,CO和DNOAF蒸汽;凝聚相热分解产物主要为碳,其中还含有少量的氰酸酯基-O-C≡N。在实验基础上提出了DNOAF的热分解历程,DNOAF的热分解首先发生在呋咱环间的C-N键,然后是呋咱环的开环分解。

Synthesis of Two Furazano Azides

bis(azidomethyl) 3,3′ bis(1,2,4 oxadiazole)(Ⅰ) and bis(azidoacetamino) oxazofurazan(Ⅱ) were synthesized. The structures of these two compounds have been identified by IR, 1H NMR, MS and elemental analysis. Azido groups were introduced into furazan derivatives and energetic materials of high nitrogen content and high enthalpy of formation can be obtained. The densities of compound Ⅰ and Ⅱ are relatively high. Compound Ⅰ is an azide of lower melting point, it is hopeful to be applied as energetic plastic additives.

Synthesis of N,N'-bis(2,4-dinitrobenzofuroxan)-3,5-dinitro-2,6-diaminopyridine

N,N'-bis(2,4-dinitrobenzofuroxan)-3,5-dinitro-2,6-diaminopy- ridine has been synthesized from 2,6-diaminopyridine and trinitrodich- lorobenzene.For this compound,the structure has been determined by ele- mental analysis,IR,HNMR and MS spectroscopy.

Synthesis of N,N′-Bis(2-Nitro Benzodifuroxanyl)-1,3,5-Trinitro-2,6- Diaminobenzene

N, N’-bis (2-nitro benzodifuroxanyl)-1, 3, 5-trinitro-2, 6-diaminobenzene has been synthesized from 1, 3-dianimobenzene and trinitrotrichloro benzene. The molecular structure of this compound has been determined by elemental analysis. IR. ′HNMR, and M. S. spectroscopies.

DFT Study of Benzofuroxan Synthesis Mechanism from 2-Nitroaniline via Sodium Hypochlorite

The oxidative cyclization reaction of 2-nitroaniline via sodium hypochlorite to yield benzo- furoxan is investigated by the hybrid density functional theory B3LYP/6-31G（d,p） method. Solvent effects are estimated with the polarizable continuum model to optimize structures. The title reaction is predicted to undergo two pathways, each of which is a stepwise process. Path A includes four steps, namely oxidization, H-attack, hydrolysis, and cyclization. Path B involves the nucleophilic attack of OH^- to the H atom of the N-H bond and the proton transfer to the N atom of amino group leading to the cleavage of the N-H single bond in the amino group. The calculated results indicate that path A is favored mechanism for the title reaction. Furthermore, it is rational for one water molecule serving as a bridge to assist in the hydrolysis step of Path A and our calculations exhibit that this process is the rate-determining step.

Solubility and metastable zone width measurement of 3,4-bis (3-nitrofurazan-4-yl) furoxan (DNTF) in ethanol + water

The solubility and supersolubility of 3,4-bis(3-nitrofurazan-4-yl)furoxan(DNTF) in ethanol + water at different operation were determined by laser monitoring system under atmospheric pressure to study the metastable zone width(MSZW). The modified Apelblat equation was adopted to correlate the experimental solubility data, and the correlation result showed perfect consistent with the experimental data. The standard dissolution enthalpy, standard dissolution entropy and Gibbs energy were calculated according to the experimental solubility data. The effect of the cooling rate, stirring rate, temperature and the concentration of ethanol + water on the MSZW was studied. It was found that the MSZW of DNTF increased with the increasing cooling rate, decreasing temperature, decreasing stirring rate and decreasing ratio of water. And the apparent nucleation order of DNTF in ethanol + water was calculated by the relationship between the cooling rate and the MSZW.

Design and Selection of High Energy Materials based on 4,8-Dihydrodifurazano[3,4-b,e]pyrazine

In order to search for high energy density materials,various 4,8-dihydrodifurazano[3,4-b,e]pyrazine based energetic materials were designed.Density functional theory was employed to investigate the relationships between the structures and properties.The calculated results indicated that the properties of these designed compounds were influenced by the energetic groups and heterocyclic substituents.The-N3 energetic group was found to be the most effective substituent to improve the heats of formation of the designed compounds while the tetrazole ring/-C(NO_(2))_(3) group contributed much to the values of detonation properties.The analysis of bond orders and bond dissociation energies showed that the addition of-NHNH2,-NHNO_(2),-CH(NO_(2))_(3) and-C(NO_(2))_(3) groups would decrease the bond dissociation energies remarkably.Compounds A8,B8,C8,D8,E8,and F8 were finally screened as the potential candidates for high energy density materials since these compounds possess excellent detonation properties and acceptable thermal stabilities.Additionally,the electronic structures of the screened compounds were calculated.

Copper-catalyzed amination of phenylboronic acids with benzofurazan 1-oxides

CuCl/Phen can catalyze the C–N coupling between arylboronic acid and benzofurazan1‐oxide.This reaction occurred under mild and redox‐neutral conditions with benzofurazan1‐oxide as an aminating reagent via ring scission,leading to a bifunctionalized aminonitrobenzene.