Oxidation of Bromide by Tert‐Butyl Hypochlorite

Abstract

The kinetics of the oxidation reaction of bromide by tert‐butyl hypochlorite (tBuOCl) was studied at 25°C, ionic strength 0.5 M, and under isolation conditions. A stopped‐flow spectrophotometer was employed for monitoring the reactions. Kinetic studies show that the reaction is first order with respect to [Br−] and [tBuOCl]. Linear dependences of the proton concentration, in perchloric acid medium, and the buffer solution concentration were found on the rate constant. The activation parameters were calculated using the Arrhenius and Eyring equations from the kinetic studies performed to analyze the influence of temperature on the rate constant. The results are consistent with a reaction mechanism of general acid catalysis. The catalytic constants were obtained for the oxidation of bromide by tert‐butyl hypochlorite. The slope obtained for the Brönsted relationship was 0.36.

Bromide Oxidation: A Safe Strategy for Electrophilic Brominations

“…In a similar manner to tert ‐butyl hypochlorite being an alternative to sodium hypochlorite, tert ‐butyl hydroperoxide (TBHP) can be used as an alternative to hydrogen peroxide [68] . The results of an oxidative bromination with TBHP and HBr do not differ significantly from the same reaction with hydrogen peroxide.…”

Electrochemical Umpolung of Bromide: Transition-Metal-Free Bromination of Indole C–H Bond

“…Halogen ions, especially bromide ions, are typical nucleophiles, which are frequently used for nucleophilic substitution and addition. In order to achieve the umpolung of bromide to bromo-based electrophiles, strong chemical oxidants are regularly required [ 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 ]. However, based on the intrinsic disadvantages of chemical oxidants, such as toxicity, environmental pollution, explosion risk, and economic costs, there is a growing need for green and sustainable approaches for the umpolung of bromides.…”