We present the systematic exploration of various potential energy surfaces for systems with C6H6–x(x= 0, 1, 2, or 3) empirical formula using an automatic search approach. The primary objective of this study is to identify reaction pathways that lead to the creation of benzene,o-benzyne, and other rings. These pathways initiate with a barrierless recombination reaction and involve subsequent isomerization reactions with submerged transition states until the final product is reached. The reported reaction profiles are consistent with the existing conditions in the interstellar medium if the hot complex formed can cool down through radiative relaxation. Recent studies on the deactivation of polyaromatic hydrocarbons (PAHs) support the possibility of these reactions taking place. The C6-membered rings are considered precursors of PAHs, and our focus is on identifying pathways originating from the barrierless recombination of reactive molecules known to exist in the interstellar medium, with potential implications in other environments.