Benzimidazole Derivatives And Their Metal Complexes Carbonylation Catalytic Reaction

Nitrogen-containing heterocyclic compounds and their derivatives have been found some great application as intermediates of medicine, pesticide, dye, and some other chemical engineering's products. Benzimidazole is one of the most promising heteroaryl moiety that yielded many successful compounds with biological potential as shown by numerous reports on their various physiological actions:proton pump inhibitor(PPI), antiphlogistic, antipyretic, analgesic, spasmolytic, anti-inflammatory and antihypertensive. The application of ferrocene and the derivatives have been attached the importance in many domains, especially in the field of medicine, biochemistry, fuel, catalyzer, because of the special biological activities. All of them exhibit the wide range of biological activities, they have aroused much interest and became the focus of research.The investigation of metal-organic coordination compounds have attracted much attention for their potential applications as function material. In resent years, organo carboxylate have aroused much enormous attention driven by the aesthetic appeal of their structure diversity, biological properties and catalysis. The 2-carboxyl benzimidazole and its homologues can coordinate with divalent metal easily and efficiently synthesized many complexes exhibit fascinating structure topologies and potential applications as function materials.The purpose of the paper is to development and design a new series benzimidazole carboxylate, and coordinate with divalent metal in order to find some novel complexes with biological potential and catalytic activity which can be used as function materials. Our recent work systematically investigated the coordination chemistry of conformation benzimidazoles, and designing new coordination compounds with 2-benzimidazolelacetate and 2-benzimidazolecarboxylate.The dissertation is divided into three parts:In part one, two host compounds of ethyl 2-benzimidazolylacetate and ethyl 2-benzimidazolecarboxylate was synthesized, and introduced acetyl, benzoyl and ferrocenylformylglycine on 1-N atom of imidazole. Furthermore six new N-substituded amide compounds has not been reported were synthesized use ethyl 2-benzimidazolylacetate and ethyl 2-benzimidazolecarboxylate as the basis, as follows ethyl 1-acetyl-2-benzimidazolylacetate, ethyl 1-benzoyl-2-benzimidazolylacetate, ethyl 1-ferrocenylformylglycine-2-benzimidazolylacetate, ethyl 1-acetyl-2-benzimidazolecarboxylate, ethyl 1-benzoyl-2-benzimidazolecarboxylate, ethyl 1-ferrocenylformylglycine-2-benzimidazolecarboxylate. Their structures were characterized by IR,1H NMR and elemental analysis. Also the optimum reaction condition and the synthesis of the compounds were disscessed.In parts two, a series of metal-organic compounds were synthesized. They were synthesezd by the reactions of Co, Ni, Zn, Cd salts with ethyl 2-benzimidazolylacetate or ethyl 2-benzimidazolecarboxylate. Our work systematically investigated the coordination chemistry and conformation characteristic of ethyl 2-benzimidazolylacetate or ethyl 2-benzimidazolecarboxylate, and coordination behavior, such as coordination abilities, coordination modes and the structures of complexes of the ligand completely, and research the possible influence factors to the produces under different reaction condition. All of these compounds were characterization by different chemical analysis methods. Four single crystal of the compounds were developed and structurally characterized by Single-crystal X-ray diffractometer, and the coordination modes and the structures of complexes were discussed. The structures of other four complexes were inferred by IR spectroscopy. All of the eight complexes were characterized by IR spectroscopy, elemental analysis, solid-state luminescent properties and thermogravimetric (TG) analysis. We systematically study on the coordination behavior of benzimidazoles, and the interaction between the metal and ligands, also disscessed the exhibition of behavior and characteristic in the synthesis of complexes.In part three, the synthesis of phenylacetic acid from the carbonylation of benzyl chlorine catalyzed by Co, Ni, Zn Cd, metal complexes have been synthesized was studied. The carbonylation catalytic active of ethyl 2-benzimidazolylacetate or ethyl 2-benzimidazolecarboxylate cobalt complexes were systematically discussed in this paper, and acquired high yield in phenylacetic acid. Improve the experimental process taking by orthogonal testing method. The effects of phase transfer catalysts, solvents, reaction temperature and the concentration of alkali on the reactions were investigated, and taking out a feaible system of catalysis experiment. The effection of experiment conditions were meticulosity analyzed, all of this provided the theoretical basis for large-scale preparations experiment, and we have taken out a method for catalyst reactivation. Then the carbonylation catalytic active of ethyl 2-benzoxazolylacetate cobalt complexes were systematically discussed in synthesis of phenylacetic acid, we were surprised to find that ethyl 2-benzoxazolylacetate showing excellent catalytic active in the synthesis of phenylacetic acid from the carbonylation catalytic of benzyl chlorine.