Multicomponent Tandem Polymerization Of Phenyl-propynyl Sulfonamide,Aromatic Alkyne And Amine Or Thiol And Its Polymerization Results Properties Study

Multicomponent polymerizations?MCPs?as a burgeoning field in polymer chemistry has proved to be a powerful and popular tool for the construction of functional polymer materials with diverse and complex structures.To explore the general applicability of MCPs and enrich the product structures of MCPs,multicomponent tandem polymerizations?MCTPs?with great synthetic simplicity and efficiency were pursued.In this thesis,MCTPs of N-?2-iodophenyl?-3-phenyl-N-tosylpropiolamide,aromatic terminal alkynes,and diamines were explored through the combination of Sonogashira coupling and Michael addition reaction in a one-pot procedure.The MCTPs could proceed efficiently and conveniently at mild condition in the presence of Pd?PPh₃?₂Cl₂,CuI,and i-Pr₂NEt,affording 12 poly?indolone?s with unique structures and high M_ws?up to 30400 g/mol?in high yields?up to 97%?.All these polymers enjoy good to excellent solubility and satisfactory thermal stability.The poly?indolone?s possess a unique acid-triggered fluorescence“turn-on”response which could realize specific detection of CF₃SO₃H from other inorganic and organic acids through a rapid acid-catalyzed reaction from enamine to ketone.Thiol as a better nucleophilic reagent than amine,which should be suitable for the above-mentioned multicomponent tandem reaction/polymerization.However,because of the side reactions that may take place with thiol,similar reactions have not been reported yet.In this thesis,through optimization of the condition,we succeed in expanding the third-component reactant from amine to thiol in the multicomponent tandem reaction of N-?2-iodophenyl?-3-phenyl-N-tosylpropiolamide,aromatic terminal alkynes,and nucleophile,affording vinyl sulfide group-containing poly?indolone?derivatives.Furthermore,the MCTP of N-?2-iodophenyl?-3-phenyl-N-tosylpropiolamide,aromatic terminal alkynes,and dithiols were explored under mild condition in the presence of Pd?PPh₃?₂Cl₂,CuI,and i-Pr₂NEt,affording12 vinyl sulfide group-containing poly?indolone?s with unique structures and high M_ws?up to20300 g/mol?in high yields?up to 83%?.All these polymers enjoy good solubility and satisfactory thermal stability,and the large number of sulfur atoms have endowed the polymers with high refractivity.The vinyl sulfide groups in model compounds and polymers can be oxidized in the presence of m-chloroperoxybenzoic acid.The oxidation products exhibit aggregation-induced emission properties,which also show enhanced hydrophilicity.With the unique structure and property,chiral polymers has found great potential in biological application,optoelectronic devices,and self-assembly.However,the efficient construction of chiral polymers is always a challenge faced by polymer synthetic chemists.In this thesis,we tried to use the newly developed MCTP to prepare chiral polymers by utilizing a pair of 1,2-cyclohexanediamine enantiomers as the third component monomer.Through the MCTPs of N-?2-iodophenyl?-3-phenyl-N-tosylpropiolamide,two kinds of aromatic terminal diynes,and the chiral diamine enantiomers in the presence of Pd?PPh₃?₂Cl₂,CuI,and i-Pr₂NEt,two pair of enamine moiety-containing chiral oligo?indolone?s were obtained.Obvious cotton effect was observed for the chiral oligomers from circular dichroism?CD?spectra.In addition,the degradation of oligo?indolone?s under acidic condition can be monitored by CD signals.In summary,we successfully developed a new type of multicomponent tandem polymerization,which was based on N-?2-iodophenyl?-3-phenyl-N-tosylpropiolamide,aromatic diynes and nucleophiles?amines or thiols?.The poly?indolone?products with acid-triggered fluorescence response,high refractive index,and chiral properties could be facilely obtained.This MCTP is convenient and efficient,showing great potential in the construction of functional polymer materials with complex structure,rich heteroatoms,heterocycles,or fused heterocycles.