Abstract: Base-catalyzed decomposition of a-hydroperoxy nitriles RI R2C (OOH) CN, 1, has been studied kinetically in MeOH or water and chemiluminescence is observed by addition of a suitable fluorescer. The reaction with 0.1 M MeONa is completed within 2 h at 25 OC, affording 75-100% yields of ketones, R, R2C= O, and OCN-. The reaction satisfies first-order kinetics with respect to 1 and the rate constant increases with increasing pH, approaching ...