Synthesis Of Cucurbituril And Glycoluril Derivatives

Cucurbit[6]uril(CB[6])is a highly symmetrical hollow macrocyclic compound,which is composed of 6 units of glycoluril linked by 12 methylene bridges.It is a highly symmetrically rigid and very stable molecule.It is well known in many fields such as supramolecular polymers,drug delivery,catalytic reaction and environmental protection.However,the poor solubility of cucurbituril and the difficulty of derivatization seriously delay the development of cucurbituril.Based on the investigation of literatures,the modified method of cucurbituril and its derivatives was optimized,that is,the synthesis of cucurbituril with the template of KCl method.In addition,based on the previous achievements of the laboratory,some propeller-type tricyclic glycoluril derivatives were synthesized and the substrate was extended.The structures of these derivatives were also characterized.The specific conclusions and innovative achievements are shown as follows:The results showed that Cucurbit[n]uril(n = 5,6,7,8)was synthesized with the template of KCl by water-hydrochloric acid-acetone separation method as the raw material.According to the analysis of TLC,only CB[6] was found.Then the reaction temperature,reaction time and the amount of the reaction raw materials were investigated.The results showed that it can be repeated at the condition of 110 g glycoluril heating at 108? for 2 hours,then cooled to room temperature over 12 h.The solid obtained by filtration was washed with acetone,and be confirmed as CB[6].The analysis of Cucurbituril obtained in this paper showed that the yield of this method was much lower than that of the traditional method.The result of this experiment was speculated as an experimental phenomenon during the reaction process.This method saves a lot of separation time and the amount of acid,after all,is a more environmentally friendly approach.Based on the previous achievements of the laboratory,a series of of substituted glycoluril derivatives was synthesized by microwave.In order to synthesize efficiently,the synthesis of N,N'-disubstituted glycoluril have been improved.Using p-toluenesulfonic acid as the catalyst,the substituted tricyclic glycoluril derivatives named monosubstituted 3,7,9,11-tetraoxy-2,4,6,8,10-pentaaza[3.3.3]propane compound was synthesized.Next,the substituted glycoluril diether was prepared by using the above products as raw materials.In trifluoroacetic acid,the glycoluril derivatives were self-condensed with paraformaldehyde and the two N-H groups were connected by a diether bond.The experimental results showed that,in addition to the target product,two by-products with three and four ether linkages was found,and be confirmed by NMR and mass spectrum.The reaction conditions were optimized.IR,NMR and mass spectrum confirmed the structures of all products.