The autoxidation of trimethylamine in aqueous solutions has been studied at 100°C and at O2 pressures up to 153 atm. Trimethylamine N-oxide is a major product. Its yield accounts for as much as, but never in excess of 50%, the balance being Me2NH and HCONMe2. The reaction follows second-order kinetics, -d[Me3N]/dt = k[Me3N]Po2, where k = 8.7 × 10-7 atm-1 s-1. In solutions buffered with 0.1 N NaOH, the yield of Me3NO is reduced. These results are interpreted in terms of a rate-limiting electron-transfer reaction between Me3N and dioxygen, followed by reactions dictated by the radical ions, Me3N.+ and O2 .-, thus generated. It is noted that only one oxygen atom in the O2 molecule is incorporated into Me3NO, the other being used in the sacrificial oxidations to give other products.
|Number of pages||4|
|Journal||Journal of Organic Chemistry|
|Publication status||Published - 1990|
ASJC Scopus subject areas
- Organic Chemistry