Study On The Amylation Reaction Of Benzoazoles And The Modification Of Pyridine Compounds With Sp ~ 2C - H

2-(Arylthio)aniline、 2-aryloxyaniline and pyridinecarboxamides are two types of important organic intermediates. The methods of the synthesis of the compounds have been caused a great considerable attention. But so far, a general, efficient and environme ntally friendly synthetic method of these two types of compounds has not been reported yet. This paper consists of two parts. (1) a new method of preparing 2-(aryl-thio)anilines and 2-phenoxyaniline was developed. (2) a new method of preparing the pyridinecarboxamides was developed.The main contents are as follows:a new method of preparing 2-(arylthio) anilineand 2-aryloxyaniline by ring-opening arylation of the benzazoles with aryl iodides was developed. The reaction of benzothiazole and iodobenzene was selected as a model reaction. We optimized solvent, catalyst and base. The combination of copper power and cesium carbonate in PEG gave the best result. Under the optimised conditions, we employed benzothiazole,6-nitrobenzothiazole,6-methyl-benzothiazole as substrates with aryl iodides to afford 2-(arylthio)aniline and 2-aryloxyaniline in 79%-96% yields. We made a TEM anylysis to prove that the reaction system is a nanocatalysis. Gratifyingly, the in situ formed catalyst can be recycled up to five times to in 90% average yield, yield. Finally, a preliminary mechanism was researched.A novel method of preparing pyridinecarboxamides was developed. The transformation undergoes two-fold C-H bond activation in the presence of a silver catalyst. The reaction between isonicotinate and formamide was chosen as the standard reaction to optimize reaction parameters. The best result were obtained when the reaction was carried with silver nitrate as catalyst, sodium formate as base, and potassium persulfate as oxidant in formamide at 80℃. Under the standard conditions, a series of pyridinecarboxamides were synthesized in good to excellant yields. Extra water can contribute to improve reaction selectivity. Additionally, we undertook a preliminary study on the mechanism of the reaction.