Highly efficient solvent-free coupling reaction of carbon dioxide(CO2)and epichlorohydrin catalyzed by meso-tetraphenyl porphyrin magnesium(MgTPP)in the presence of triethylamine as co-catalysts is reported.As a chlorophyll-like catalyst,MgTPP showed excellent activity for the coupling reaction of CO2 and epichlorohydrin to chloropropene carbonate,in which the turnover number could reach up to 9200.Moreover,different factors including the amount of catalyst,reaction temperature,pressure and time were systematically investigated and the optimal reaction conditions were obtained(epichlorohydrin 50 mmol,MgTPP 5.0×10- 3mmol,triethylamine 6.25×10-3 mmol,140°C,1.5 MPa,8 h).A plausible two-pathway mechanism for the coupling reaction of CO 2and epichlorohydrin is proposed to propound the catalysis of MgTPP.
The two novel green oxidation processes of p/o-cresols to p/o-hydroxybenzaldehydes catalyzed by metalloporphyrins in the presence of molecular oxygen were developed in this work.Among the metalloporphyrins with different central ions and substituents studied,T(p-NO 2)PPCoCl and T(p-OCH 3)PPFeCl presented the highest activities for p-cresol and o-cresol oxidation reactions respectively.The molar ratio of sodium hydroxide to cresols and different reaction parameters including reaction temperature,reaction time and reaction pressure have been investigated,and 69.8%/50.4% conversions of p/o-cresol and 86.6%/26.6% selectivities for p/o-hydroxybenzaldehydes were reached under optimized conditions.
