Study On The Preparation Of Isonitrile Derivatives And Related Properties

As the isomer of nitrile compounds,isonitrile compounds(-NC)with characteristics of both electrophilic and nucleophilic,special metal-binding capability and could be polymerized under mild conditions,and thus have been widely used in organic synthesis,organic-metal complexes preparation and polymer construction.In this thesis,a series of isonitrile compounds were successfully prepared by N-substituted formamide dehydration or Hofmann methods.The optical properties,difunctional isonitrile polymerization and novel reaction between isonitrile-benzoxazine were studied here from the following aspects:1.A type of isonitrile compound(M2)was successfully prepared with 3-nitro-1,8-naphthalicanhydride as starting compound via N-substituted formamide dehydration method.Optical properties of M2 were studied by UV-Vis spectrophotometer and fluorospectrophotometer.Ratiometric alteration was clearly detected after the addition of Hg2+to M2 solution in VTHF/Vwater= 3/7 co-solvent system.Its fluorescence did not change significantly after the addition of other common anions and cations.According to fluorescence spectra of M2 towards incremental Hg2+,the detection limit of M2 to Hg2+ can be evaluated as?9.1 ×10-8 M.Application of M2 to detect Hg2+ in real water samples and M2-supported agarose gels revealed that M2 has the potential to act as selective Hg2+ optical probe.2.A series of isonitrile compounds with different structures(IC1-IC5)were successfully prepared by N-substituted formamide dehydration or Hofmann methods,and the optimal reaction conditions of metal-catalyzed isonitrile-polymerization were screened out by using odorless,chemical stable,aromatic bifunctional isonitrile compound,IC5,as starting monomer.Experimental results tell that the optimal reaction conditions for Pd(?)-catalyzed IC5 polymerization were:THF as solvent,reaction temperature is 55?,reaction time is 24h,and the yield can reach 77%.The optimal reaction conditions for Ni(?)-catalyzed IC5 polymerization were:CHCl3 as solvent,reaction temperature is 60?,reaction time is 12h,and the yield can reach 65%.Brunauer-Emmett-Teller(BET)investigation indicated that as compared to P1-Ni(?),P1-Pd(?)possesses larger specific surface area and pore volume.3.A series of comb-like aggregation-induced enhanced emission(AIEE)-type isonitrile-benzoxazine polymers(P3)were prepared through post-modification of polybenzoxazine-derivatived polymer by using AIEE-type isonitrile compound IC6 and the bisphenol A-based benzoxazine polymer(P2)as starting materials.The influence brought by the feeding ratio of P2/IC6 to the reaction degree was investigated by FT-IR and gel permeation chromatography(GPC)analyses,confirming the successful implementation of polymer structure modification.The polymer P3-3,which with the highest number-average molecular weight and higher post-polymerization decoration degree,has been selected here to achieve Ag+ detection in THF/H2O(V/V=4:6)co-solvent system.This investigation provides a successful example for the construction of functional polymers through the functional-groups-reaction between isonitrile and benzoxazine.