卤甲基芳烃和三卤甲基芳烃合成分析-synthesis and analysis of halomethyl aromatic hydrocarbon and trihalomethyl aromatic hydrocarbon.docx

Synthesis of trichloromethylated aromatic compounds. Trichloromethylation reaction of aromatic carboxylic acids or aroylchlorides has been accomplished by using tetrachlorophenylphosphine or dichlorophenylphosphine/phosphoric chloride as the transforming agent. The trichloromethylation reaction can be well controlled and the phenylphosphonic dichloride produced in the process can be reclaimed for reuse. A series of trichloromethylated aromatics including two new compounds, such as 3-trichloromethylbromobenzene and 2-trichloromethylmethbenzenetoluene, have been synthesized. The influences and the mechanism of the reaction have also been studied. It was found that the reaction was accelerated obviously with the electron-pushing groups attached to dichlorophenylphosphine and was decreased with the electron- withdrawing groups attached. On the other hand, the effects of substituents of the aromatic acids (or aroylchloride) on the reaction were opposed.Preparation of benzyl bromide derivatives. A facile method for the benzylic monobromination of toluene derivatives has been developed using boron tribromide as bromine source at ambient temperature. The best conditions for boron tribromide mediated benzylic bromination were defined using toluene as model substrate. It is found that increasing temperature resulted in decreasing in the yield of benzyl bromide, but slightly increased the yield of benzal bromide. Similarly, increasing the equivalence of boron tribromide caused an increase in the yield of benzal bromide. In addition, the solvent has shown a dramatic influence on the bromination yields. Increasing the solvating power of solvent decreased the benzyl bromide yield. Alkylbenzenes with electron-pushing group on the aromatic ring were found to convert into their corresponding benzyl bromides in high yields. Under identical conditions, deactivated toluene derivatives afforded lower quantities amount of benzyl bromides. This bromiantion approach seems to have an ionic