tert‐butanol and hydrogen peroxide react over Amberlyst‐15 to form tert‐butyl hydroperoxide

Abstract

AbstractOrganic peroxides are explosive compounds that are applied as disinfectants, bleaching agents, and as initiators for polymer synthesis because of their high reactivity. Traditional homogeneous processes with H2SO4 catalyst produce salts, either in the neturalization step after reaction or due to the foramtion of tert‐butyl hydrogen sulphate, that must be disposed of, which introduces cost and represents an environmental burden. Here, we devised a flow chemistry approach to oxidize tert‐butyl alcohol (TBA) to tert‐butyl hydroperoxide (TBHP) over various heterogeneous catalysts. Under acidic conditions, TBHP is the main product and di‐tert‐butyl peroxide (DTBP) and peroxy‐ketal are by‐products. The most active catalyst was Amberlyst‐15, while yield of Nafion, activated carbon, and heteropoly acids (HPA) on carbon and silica matrices was less than 1% at 70°C. In in the range of 30 to 50°C, a first order kinetic expression characterizes the tert‐butyl alcohol conversion well (). The reaction rate is slow and the rate constant, , was 0.003 min−1. Above 50°C, by‐products reacted further to acetone, methane, ethane, and other compounds.