The continuous-flow microreactor technique for the synthesis of bicyclic esters is reported in this paper. The synthesis time of bicyclic esters can be greatly shortened by the continuous-flow technique, and the advantage of continuous-flow microreactor is analyzed theoretically. Taking the synthesis of bicyclo[2,2,1]-5-hepten-2-methyl ester as an example, the molar ratio between cyclopentadiene (A) and methyl acrylate (B) is 1.1 to 1, the temperature is 353 K, the reaction time is 335 s, the yield reached 96.7% in a continuous-flow microreactor. However, it takes 4.5 hours to synthesize the compound within batch reaction, and the yield is 93%. It is of significant to change the batch reaction into continuous production both in the laboratory and industrial production.

The pentacyclic‐[8.2.1.14,702,903,8]‐tetradecane‐5,6,11,12‐tetracarboxylic dianhydride was prepared by norbornene dianhydrides as raw material and acetone as a solvent in a self‐made vertical photo reactor with single wavelength ultraviolet light. Based on the Gaussian Calculation combine with experiments, we studied the optimum wavelength of ultraviolet light and the stable conformation of the target product. The structure of the target compound was determined by HPLC‐MS, 1H NMR, 13C NMR, and X‐ray diffraction. The results showed that the yield of pentacyclic‐[8.2.1.14,702,903,8]‐tetradecane‐5,6,11,12‐tetracarboxylic dianhydride could reach 50.5 %, the reaction temperature was 20 °C, the initial concentration of reactant was 0.15 g/mL, the flow rate of the substrate was 5 mL/min, and the reaction time was 4 h.