Synthesis And Properties Of Novel Tripod - Type Polybenzimidazole Quaternary Ammonium Salts

Compounds containing benzimidazole skeleton, have extensive biological activities, such as antibacterial, antiviral, anti-inflammatory and anti-cancer in medicine, herbicidal and plant growth in pesticides and other aspects. Studies showed that the quaternary ammonium salt containing benzimidazole skeleton could also become excellent anion recognition probe. A new kind of molecules with three foot type, complicated functional properties was synthesized for the first time through simple and efficient method. The application of the target molecules in medicine, pesticides, anion recognition and the anion recognition process was texplored. The detail contents are as follows:Firstly, compounds containing benzimidazole unit has been widely applied to medicine and pesticide because of its high efficiency, low toxicity. Base on the principle of superposition of the drug, the key intermediates TBM were afforded through the reaction of tris(2-chloroethyl)amine with benzimidazole.25New target products TBMQ were first synthesized by the reaction of TBM with different substituted benzyl chloride The optimal synthetic conditions of TBM and TBMQ were explored:tris(2-chloroethyl)amine (mol/mol)=3.2:1, tetrahydrofuran as solvent, NaH as the base, the temperature was70℃, the reaction time was4h, the yield reached to88%. And the optimal conditions of TBMQ were as follow: reaction temperature was110℃, DMF as solvent, reaction time was48h, the obtained yield rate was up to78%. And the structures were characterized by IR,1H NMR,13C HMR and HRMS, the results showed that the compounds were synthesized successfully.Secondly, the drug activities of25target products TBMQ were performed. The inhibitory activities of TBMQ on protein tyrosine phosphatase (PTP1B) and Cell cycle division protease (Cdc25B) showed that molecules containing amino group, pyridine unit, chlorine and fluorine atoms had certain antitumor activities, especially the molecule TBMQ-19(IC50=0.31±0.05), which was superior to the contrast oleanolic acid (IC50=1.27±0.19) and molecules containing amino group, indole group, pyridine unit, chlorine and fluorine atoms had certain antitumor activities, especially the molecule TBMQ-14(IC50=0.65±0.12), which was superior to the contrast sodium orthavanadium (IC50=1.86±0.24). This result means TBMQ-14ws expected to be inhibitors of Cdc25B This result means TBMQ-19and TBMQ-14were expected to be inhibitors of PTP1B and Cdc25B, provides an important reference for the development of diabetes drugs.Thirdly, the plant growth regulator andherbicidal activities of TBMQ were tested. The results of cytokinin activity by cucumber cotyledon rooting method showed that20compounds exhibited excellent promotin, TBMQ-19was the best up to90.3%; the results of wheat coleoptile of auxin activity promotion show that TBMQ-19had the highest activity up to47.8%, the other compounds also showed certain activity. In the study of barnyard grass herbicidal activity, all target molecules showed definite inhibition, TBMQ-10containing nitro group was the best up to95.6%. These results showed that the target molecules with novel structure had potential applications in pesticide application.Finally, the target products in anion recognition were discussed. The fluorescence properties were performed under concentration of1×10-5mol/L of target compounds and concentration of2×104mol/L of F-,Cl-,Br-, I-,H2PO4-and CH3COO-. The results showed that I-produced efficient quenching effect, indicating that the target compounds TBMQ could be used as fluorescence probe of I-recognition. Meanwhile, the quenching mechaniMS of I-was studied by UV absorption data:the results showed that the addition of I-did not produce displacement ultraviolet absorption peak, and the temperature dependent fluorescence test results also showed that quenching rate increased with increasing temperature,1HNMR also apparent displacement did not occur suggesting that I-quenching mechaniMS was dynamic quenching.