Experimental and Theoretical Investigation of 2-Methylbenzothiazole Oxidation by OH in Air and the Role of O2 and NO.

Abstract

Benzothiazoles are in widespread use as components of, or precursors to, a variety of consumer and industrial products. This class of compounds encompasses the simplest molecule benzothiazole (BTH) in which a benzene ring is fused to a thiazole ring, as well as a series of derivatives which are commonly functionalized at the C2 position of the thiazole ring. The addition of groups at this position modifies the reactivity in ways that are not well-known. While the reactions of benzothiazoles in water have been the subject of investigation, in part for wastewater treatment applications, much less is known about their atmospheric reactions where gas phase oxidation by the OH radical is expected to dominate. We report here studies of the kinetics, products, and mechanism of reaction of 2-methylbenzothiazole (MeBTH) with OH in the gas phase using a combination of experiments and theory. Comparison to previous studies of the OH oxidation of BTH highlights the impact of substitution of a methyl group at the 2-position on the products and reactivity. Specifically, the rate constant at 298 K and 1 atm pressure for the MeBTH-OH reaction is (3.0 ± 0.4) × 10^-12 cm³ molecule^-1 s^-1 (1σ), about 50% faster than that of BTH. In addition, attack of OH on the -CH₃ group at the 2-position of the thiazole ring to form the aldehyde as the stable product becomes important, accounting for ∼ 33% of the overall reaction. Formation of the phenol-type products from attack on the benzene ring accounts for the remainder, with the experimental relative yields consistent with theoretical predictions based on energies of formation of the prereaction MeBTH···OH complex. The formation of the aldehyde product (2-CHO-BTH) involves a sequence of five distinct stages involving two oxygen molecules and one NO. Both processes involve a spin flip of unpaired electrons, which enables a transition between electronic states that is essential for the reaction to proceed. Using the room temperature rate constant, the estimated lifetimes of MeBTH in air range from about 9 h to 4 days over OH concentrations of 10⁷ - 10⁶ cm^-3. Thus, this reaction represents a significant loss process for MeBTH in air both outdoors and indoors, and exposures and toxicity of both the parent MeBTH and its oxidation products need to be taken into account in assessments of its environmental fates.