Direct access to alkyl-substituted pyrazine Noxides has been accomplished through an intermolecular dehydrogenative cross-couplingr eaction of ethers and pyrazine N-oxides in the presence of tert-butyl hydroperoxide (TBHP). This approach successfully provided av ariety of alkyl-substituted pyrazine N-oxides in up to 96 %y ield. Thermogravimetric analysis indicates that the degradation tem-perature of C2-alkyated product 3a is approximately 263 8C. Under pyrolysisc onditions, 3a generated several compoundss uch as 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, and 3-ethyl-2,5-dimethylpyrazine, which are characterized by their distinct aromas. The results of the pyrolysis experiment support the use of these compounds as possible flavor additives.