Abstract
Relative rate coefficients for the reactions of OH with 3‐methyl‐2‐cyclohexen‐1‐one and 3,5,5‐trimethyl‐2‐cyclohexen‐1‐one have been determined at 298 K and atmospheric pressure by the relative rate technique. OH radicals were generated by the photolysis of methyl nitrite in synthetic air mixtures containing ppm levels of nitric oxide together with the test and reference substrates. The concentrations of the test and reference substrates were followed by gas chromatography. Based on the value k(OH + cyclohexene) = (6.77 ± 1.35) × 10^−11^ cm^3^ molecule^−1^ s^−1^, rate coefficients for k(OH + 3‐methyl‐2‐cyclohexen‐1‐one) = (3.1 ± 1.0) × 10^−11^ and k(OH + 3,5,5‐trimethyl‐2‐cyclohexen‐1‐one) = (2.4 ± 0.7) × 10^−11^ cm^3^ molecule^−1^ s^−1^ were determined. To test the system we also measured k(OH + isoprene) = (1.11 ± 0.23) × 10^−10^ cm^3^ molecule^−1^ s^−1^, relative to the value k(OH + (E)‐2‐butene) = (6.4 ± 1.28) × 10^−11^ cm^3^ molecule^−1^ s^−1^. The results are discussed in terms of structure–activity relationships, and the reactivities of cyclic ketones formed in the photo‐oxidation of monoterpene are estimated. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 7–11, 2002