A green catalyst-free concomitant air oxidation of DMSO and cumene to form methylsulfonylmethane (dimethylsulfone)

Methylsulfonylmethane (MSM) is a newly discovered human nutrient that has significant health care and therapeutic function. In this work, we developed a new type of catalyst-free air oxidation of dimethyl sulfoxide (DMSO) to MSM under relatively mild conditions based on the mechanism of isopropylphenyl free radicals (R center dot) activating molecular oxygen (O-2) generating reactive oxygen species (ROS). Experimental results showed that cumene as a solvent, due to its active tertiary sp(3) C-H bond, promotes the efficient catalyst-free air oxidation of DMSO to MSM under relatively mild optimized conditions. Based on the quenching test of free radicals and theoretical calculation of the activation energies of two oxidation pathways of isopropylphenyl peroxy radicals (ROO center dot) and cumene hydroperoxide (CHP), it has been demonstrated that ROS in this reaction is mainly ROO center dot and hydroxyl radicals (HO center dot). Furthermore, we proposed a possible catalyst-free air oxidation mechanism. This work provided a simple and cost-efficient approach for the green synthesis of MSM.

Automated summary

A novel catalysis-free air oxidation method for the synthesis of MSM was developed based on the activation of molecular oxygen by isopropylphenyl free radicals, showing a simple and cost-efficient approach for the green synthesis of MSM under relatively mild conditions. This research provided insights into the mechanism of ROS generation and the efficient conversion of DMSO to MSM.