The bulk polymerization of benzonitrile catalyzed by Co(Ⅱ), Co(Ⅲ) and Fe(Ⅲ) acetylacetonate was studied. The results of kinetics study show that the rate of polymerization was proportional to first power of the con...The bulk polymerization of benzonitrile catalyzed by Co(Ⅱ), Co(Ⅲ) and Fe(Ⅲ) acetylacetonate was studied. The results of kinetics study show that the rate of polymerization was proportional to first power of the concentration of catalyst and second power of the concentration of monomer.展开更多
Metal acetylacetonates,a type of readily synthesized or commercially available metal complex,were demonstrated to be robust catalysts for the synthesis of oxazolidinone from CO_(2);aziridine under condition of atmosph...Metal acetylacetonates,a type of readily synthesized or commercially available metal complex,were demonstrated to be robust catalysts for the synthesis of oxazolidinone from CO_(2);aziridine under condition of atmospheric pressure and mild temperature,exhibiting high chemo- and regio-selectivity.Tetrabutylammonium halides were employed as cocatalysts in the reaction,and it was believed that the reaction activity was influenced by a balance of anions’ two abilities,namely their nucleophilicity in ring-opening of aziridines and their leaving capacity in ring-closing of intermediate carbamate salts to form oxazolidinones.Notably,higher nucleophilicity of these anions resulted in increased formation of dimers,which served as by-products of the reaction.The study of mechanism suggested that there should be an alternative pathway involving CO_(2) derivative acting as a nucleophile during the ring-opening process,and this pathway could not be ignored when conventional nucleophiles,such as tetrabutylammonium halides are absent.展开更多
文摘The bulk polymerization of benzonitrile catalyzed by Co(Ⅱ), Co(Ⅲ) and Fe(Ⅲ) acetylacetonate was studied. The results of kinetics study show that the rate of polymerization was proportional to first power of the concentration of catalyst and second power of the concentration of monomer.
基金supported by the Program for Public Technology of Jiaxing Province,China (No.2023AD11041)the Natural Science Foundation of Zhejiang Province,China (No.LY22E020009)+1 种基金the National Undergraduate Training Programs for Innovation of China (No.202110354038)the Student Research Training Program of Jiaxing University,China (No.8517231462).
文摘Metal acetylacetonates,a type of readily synthesized or commercially available metal complex,were demonstrated to be robust catalysts for the synthesis of oxazolidinone from CO_(2);aziridine under condition of atmospheric pressure and mild temperature,exhibiting high chemo- and regio-selectivity.Tetrabutylammonium halides were employed as cocatalysts in the reaction,and it was believed that the reaction activity was influenced by a balance of anions’ two abilities,namely their nucleophilicity in ring-opening of aziridines and their leaving capacity in ring-closing of intermediate carbamate salts to form oxazolidinones.Notably,higher nucleophilicity of these anions resulted in increased formation of dimers,which served as by-products of the reaction.The study of mechanism suggested that there should be an alternative pathway involving CO_(2) derivative acting as a nucleophile during the ring-opening process,and this pathway could not be ignored when conventional nucleophiles,such as tetrabutylammonium halides are absent.
