More detailed kinetic modeling of the parallel reactions (A) and (B) involving reagents PhCNO and PhNSO predicts reaction (A) to be the main pathway, which is in line with the previously obtained experimental data. Furthermore, non-negligible amounts (7% at 298 K, 12% at 383 K) of the corresponding product are predicted to form via the pathway (B). Thus, it is hypothesized that the PhNSO compound formerly obtained in 14-18% yield in benzene is a product of the parallel reaction (B) and not the unreacted reagent. It should be noted that upon changing the solvent from benzene to diethyl ether, the reagents are not purified from the final reaction mixture. These observations are consistent with the results of in silico investigations: barrier heights of the first reaction steps (determining the ratio of the final product) in the pathways (A) and (B) are predicted to differ by 1.5 and 2.2 kcal/mol for reactions in benzene and in THF, respectively. The difference between the barrier heights determines the higher selectivity for reaction in THF compared to that in benzene. The explicit kinetic modeling was based on the rate constants calculated with the Eyring-Polanyi equation, which uses the Gibbs free energies of the transition states. These values were obtained with the state-of-the-art ab-initio method DLPNO-CCSD(T)/CBS//ωB97X-D3(BJ)/def2-TZVP in CPCM(THF). ) for the substituted phenylnitrile oxides. The x-axis denotes the substitution position. A solid horizontal line is an effective barrier for the unsubstituted species (12 kcal/mol).