Design And Synthesis Of High-performance Polymeric Benzoylating Reagents By Controlled Polymerization

Polymer-supported acylating reagents are excellent acyl transfer reagents for the amino-containing organic compounds and have significant applications in the fields such as the synthesis of drugs and drug intermediates, fine chemistry, sewage treatment and so on. Living Ring Opening Metathesis Polymerization (Living-ROMP) and Atom Transfer Radical Polymerization (ATRP) are two kinds of important"living"/controllable polymerizations, and both of the two reactions can be used for designing, tailoring and synthesizing polymers with controlled components and different microcosmic topological structures.The following creative research work was conducted and reported in this master's thesis:1. The synthesis of exo-N-benzoyloxy-7-oxabicyclo[2.2.1]hept-5-ene-2,3--dicarboximide (monomer BOHD).2. Soluable microgel-supported benzoylating reagents with high molecular weight [Mn=(3.84-4.21)×105] and low cross-link degree (4.5%-4.8%), which could be easily recovered, regenerated and reused, were synthesized by combined Living-ROMP and Activator Regenerated by Electron Transfer for ATRP (ARGET ATRP). These microgel-supported benzoylating reagents showed excellent benzoyl-transfer ability for aliphatic primary amine and secondary amine with very high yield and purity of the product N-benzoylamines.3. Soluable three-arm star-shaped polymeric benzoylating reagents [Mn= (4.79-5.06)×104, PDI=1.23-1.29] and soluable microgel-supported benzoylating reagents [Mn=(5.59-5.62)×104, PDI= 1.94-2.07] were synthesized by Living-ROMP; A bead-like polymeric benzoylating reagent with particle diameter is 0.2-0.3 mm was synthesized by the combined ROMP-shape formation of suspension-radical polymerization.4. A bead-form polymeric benzoylating reagent was synthesized by ATRP of the monomer BOHD, which could be initiated by the commercial chloromethylated polystyrene resin used as a solid-supported initiator, and the reaction condition as optimizated. In the optimizated reaction condition the monomer BOHD conversion was increased to 86.0%.