Hydrazine With Carbonyl Compounds By Solid State Reaction And Its Mechanism

The reaction of the hydrazine with the aldehyde (or ketone) always leads to the formation of a hydrazone, which is an important compound because of its activation in biology and pharmacology. For example, 1,2,4-Triazines have been associated with diverse pharmacological activities such as antihypertension and inhibition of platelets, antileukemic, antiinflammatory, and are potent neuro-protective agents. So this reaction has attracted wide interest. The most common synthetic method of this reaction is the traditional method-reactants react in solution. In this case the reaction may cause many problems because of the present of the organic solvent, such as the environmental pollution. For avoiding the problems, solid-state synthesis are used to sythesize hydrazone in this thesis.Since solid-state synthesis has many advantages, such as manipulating easily and less pollution to environment, it develops very quickly. Recently, several new techniques, such as microwave, accelerate the development of the solid-state synthesis. In one word, solid-state synthesis is a g ood method and accords with the demand of "Green Chemistry".Althought there are many reports with regarding to the sythesis of hydrazone, to the best of our knowledge theoretical studies of the mechanism of this reaction has never b een r eported yet. In t his t hesis, t he s olid-state s ynthesis h as b een u sed t o t he reaction of the hydrazine with the aldehyde, and the mechanism of this reaction has been studied by using the ab initio and the density function methods. The thesis consists of five parts.1. Search some sood satalysts that are accord with the demand of "Green Chemistry".In the experiment, we introduced a method of solid-state synthesis: grinding the two solid reactants and catalyst together in a cornelian mortar. The reactants are p-O2N-C6H4CHO, NH2NHCSNH2, PhCONHNH2. We find some good catalysts such as NH4OAc, KF, K2CO3 except AhOs, silical gel, kaoline and so on, some of them have been reported.2. The influence of the group in phenyl to the reactionThe reactants are p-R-C6H4CHO (R=NO, H, HCK N(CH3)2) and NH2NHCSNH2, PhCONHNH2. We have studied the reaction at several condition of without catalyst or not. The results showed that the group in phenyl is great influence to the reaction.3. The mechanism of the reaction of HCHO and HCONHNH2The mechanism of the reaction of HCHO and HCONHNH2 without catalyst hasbeen examined in detail by ab initio method at HF/6-31G** level and DFT method at B3LYP/6-31G** level, obtained a stable intermediate (3) and two transition states (6 and 7). The theoretical analysis indicated that the intermediate geometry (3) is a stable structure and the transitions state (6 and 7) are all right. The potential profile for this reaction was obtained by the calculation of IRC. And we conclude that the second process is a key process of the whole reaction,At the same time, the mechanism of the reaction of HCHO and HCONHNH2 with catalyst has been also examined by ab initio method at HF/6-31G** level too, and a stable intermediate (8) and two transition states (9 and 10) have been obtained. The theoretical results have proved that the catalyst can reduce the activation energy and can accelerate the reaction. NKiAc is the best catalyst among all of catalysts we researched.4. The mechanism of the reaction of p-R-C6H4CHO(R=NO2, H, HO, N(CH3)2), and NH2NHCSNH2 or PhCONHNH2.The mechanism of the reaction of p-R-CeRtCHO (R=NO2, H, HO, N(CH3)2), and NH2NHCSNH2 or PhCONHNH2 with the catalysts or not have been studied at AMI level. The result shows that its mechanism is similar to the mechanism of the reaction of HCHO and HCONHNH2'. a stable intermediate and two transition states. The theoretical analysis also indicated that the group of phenyl has some influence at certain extent.5. The theoretical study of the isomerization of p-R-C6H4CH=NNHCSNH2 and p-R-C6H4CH=NNHCOPh (R=NO2, H, HO, N(CH3)2)The mechanism of the isomerization of p-R-C