Continuous Flow Synthesis of tert-Butyl Nitrite and Its Applications as Nitrating Agent

Herein we report a flow chemistry method for the synthesisof tert-butyl nitrite. The flow process provided95% yieldin a very short residence time of 1 min corresponding to a space timeyield of 13 g/h/mL. In addition, we used tert-butylnitrite for metal-free stereoselective nitration of alkenes. The reportedprocess had a higher batch cycle time of 12 to 24 h, limiting itsapplication for commercial production. We developed a continuous-flownitration process using a fixed bed column reactor. In the process,we provided the continuous air purging to ensure adequate supply ofoxygen in the reaction. This has helped us to reduce the reactiontime from 12 h in batch to 3 min in flow. The optimized nitrationprocess conditions were applied on a series of styrene and acrylatederivatives. The methodology has potential for industrial-scale productionof tert-butyl nitrite and its use as a nitratingagent.

Automated summary

Here, we present a flow chemistry method for synthesizing tert-butyl nitrite with a high yield of 95% and a short residence time of 1min, corresponding to a space time yield of 13 g/h/mL. In addition, we demonstrate the application of tert-butyl nitrite in metal-free stereoselective nitration of alkenes. The traditional batch process, with a cycle time of 12 to 24 h, is limited for commercial production. Therefore, we developed a continuous-flow nitration process using a fixed bed column reactor, reducing the reaction time from 12 h to 3 min and achieving a faster and more efficient synthesis.