Study On Synthesis And Performance Of Novel Heterocycles Containing Nitrogen Atom-(Z)-4-amino-5-(Hydroxyimino)-2,5-dihydro-1H-imidazole 3-oxide

To develop new reactions, new compounds and new materials is always the effortful direction of chemical workers, and to obtain valuable products by using compounds which are existing, easily available and cheap is our pursuing goal all the time. For a long time, 3,4-diaminoglyoxime (abbreviated to DAG) is widely used in the synthesis of energetic compounds, but its other reactions are seldom studied. In view of this, in this paper, a novel kind of heterocycles containing nitrogen atom was first and conveniently synthesized by the reactions of DAG with benzaldehyde derivatives, the catalytic activity of their complexes on thermal decomposition of ammonium perchlorate (abbreviated to AP) was well studied, and we found some of them have good catalytic performance.At first, nine novel nitrones were synthesized by the reactions of DAG which is easily available and benzaldehyde derivatives on mild conditions in good yield, the nitrones which are also belonged to heterocycles containing nitrogen atom are named as (Z)-4-amino-5-(hydroxyimino)-2,5-dihydro-1H-imidazole 3-oxides. Using solvent evaporation method, single crystals for five of them were obtained, the structures of them were confirmed by X-ray diffraction analysis besides IR, 1H-NMR, 13C-NMR and elemental analysis. In the structures of products, a hydroxyimino group is directly linked to the ring of imidazole, which is the first example of this type of compounds. The reaction mechanism was put forward which was mainly by two-step process of protonation and deprotonation respectively to form a five-membered heterocyclic ring. The five molecular structures are as follows: Using the nine heterocycles containing nitrogen atom to react with three acetate of Cu²⁺,Ni²⁺ and Pb²⁺ in solution separately, 27 complexes were obtained, their structures and morphology were characterized and tested by IR, elemental analysis, SEM and TEM, the results showed the complexes of 7# and 19# were nanoparticles.The thermal stability of these complexes was analyzed by DTG. We found that all the complexes were decomposed partly or entirely to yield intermediate products which were different in stability at 270℃, and some have only one intermediate which was stable and basically no weightlessness within experiment temperature, for example, the samples of 7#,8#,13# and so on. But some other complexes have two or more intermediates which were keeping decomposed while the temperature rising, for example, the samples of 4#,5#,10#,16# and so on. By synchronously thermal analysis with TG-DTG, the catalytic effect and the decomposition process were investigated on AP for all the complexes that have the same metal with different ligands and the same ligand with different metals(Cu,Ni,Pb). The results indicated that the copper complexes have the best catalytic effect, and the high temperature of decomposition is dropped 129.01℃at most, the second is nickel complexes, and the catalytic effect is the smallest for the plumbum complexes. Some complexes changed the thermal decomposition progress of AP, which made the two peaks of decomposition at its low temperature and high temperature into one, for example, the samples of copper complexes labeled 7# and 13#, the samples of nickel complexes labeled 8#, all have good catalytic effect.For the four different systems including pure AP, AP/7#, AP/13# and AP/8#, the TG-DTG data which were obtained at different heating rate were mathematically treated and analyzed by using the two kinetic equations of Kissenger and Ozawa. The results showed that the activation energy of low temperature decomposition was 132.0 (α=10%) kJ·mol-1 (Ozawa method), 198.5 kJ·mol-1 (Kissenger method) for AP/7# and 119.2 (α=10%) kJ·mol-1 (Ozawa method ), 108.8 kJ·mol-1 (Kissenger method) for AP/8#, compared with 03.3 kJ·mol-1 (Ozawa method), 112.8 kJ·mol-1 (Kissenger method) for pure AP. The results of the two kinds of calculations indicated that when the complexes were added to AP, its activation energy of low temperature decomposition is increased, so the decomposition peak was delayed; the activation energy of high temperature decomposition was 213.9 (α=40%) kJ·mol-1 (Ozawa method), 198.5 kJ·mol-1 (Kissenger method) for AP/7# and 150.3 (α=80%) kJ·mol-1 (Ozawa method ), 146.8 kJ·mol-1 (Kissenger method) for AP/8#, compared with 136.9 kJ·mol-1 (Ozawa method), 132.9 kJ·mol-1 (Kissenger method) for pure AP. Obviously, when the complexes were added to AP, its activation energy of high temperature decomposition was increased, but the high decomposition reaction was advanced and became intense. The reason might be related to the factors: the high decomposition reaction for AP was fiercely intense, the added catalyst promoted the speed of the gas-phase reaction, and so on.Compared with copper chromite, which is widely used as a burning rate catalyzer of a composite solid propellant, the 7# sample have excellent catalytic effect, but the further investigation is necessary for its practical application. The catalytic mechanism of thermal decomposition for AP is discussed. In this study, the factors that catalyze the thermal decompostion for AP are as follows: increasing the rate of electronic transfer and the series reactions in the process of the thermal decompostion for AP, and nanoparticles.The antibacterial property, the fluorescence and optical activity were tested elementarily.