Synthesis Of 1,3-Dissubstituted Benzimidazoline Derivatives And Polymer

Guanidine and its derivatives are important organic compounds,which are widely found in natural products,and variously applied in pharmaceutical industry and coordination chemistry.Because the guanidine group has many properties,therefore,the current preparation of such compounds containing multiple guanidines has become a hotspot.First of all,this thesis described a novel synthesis of bis(guanidine)s through the reaction between a solvothermally prepared benzimidazolium chloride and diamines.Secondly,the benzimidazolone-based polymers were synthesized and developed by the radical polymerization reactions of the allyl benzimidazolone.The research content and results of this thesis are as follows:1.The key intermediate benzimidazolium chloride was synthesized through a solvothermal method by a chlorine source and 1,3dimethyl-1,3-dihydro-2H-benz-imidazol-2-one(87%),which was obtained from the dimethylation of 1,3-dihydro-2H-benzimidazol-2-one in NaOH solution.The reaction condition was optimized to improve the yield of product.Then,using anhydrous chlorobenzene as a solvent and oxalyl chloride as the chlorine source,benzimidazolium chloride was prepared by a solvothermal process at 100? for 10 hours,which resulted in a yield of 92%.A series of bis(guanidine)s including aliphatic and aromatic linkers were thereafter synthesized by benzimidazolium chloride and diamines in moderate to good yield(30-78%).The intermediates and bis(guanidine)s were purified and their structures were characterized by 1H NMR,13C NMR,IR,and HRMS.2.Two allyl-substituted 1,3-dihydro-2H-benzimidazol-2-one compounds as monomers were obtained by a series of organic reactions from 1,3-dihy dro-2H-benzimidazol-2-one.Furthermore,two novel benzimidazolone-based polymers were obtained by free-radical bulk polymerizations of allyl-substituted benzimidazolone monomers.Polymerization condition was optimized.The polymers were obtained through the free radical bulk polymerization at 80? for 24 h,which was the optimal reaction condition for the polymerization.The conversion rate of the two polymers was between 51%to 69%,and the number average molecular weight of two polymers was determied to be 1341 g/mol and 3900 g/mol,respectively.The polymers were characterized by 1H NMR,IR,and GPC.3.Using two allyl-substituted 1,3-dihydro-2H-benzimidazol-2one compounds as starting marterials,the corresponding benzimidazolium chlorides were synthesized by a solvothermal method in yield of 55%and 62%,respectively.Two benzimidazolium chlorides were then used to react with aniline to give allyl-substituted guanidino monomers in yield of 75%and 83%,respectively.The guanidine-based polymers were thereafter synthesized by the allyl-substituted guanidine monomers through a free radical bulk polymerization at 80? for 24 h,The conversion rate of two polymers were 63%and 67%,and an average molecular weight of these polymers was determied to be 1370 g/mol and 2313 g/mol,respectively.The polymers were characterized by 1H NMR,IR,and GPC.