The anomaly observed has been explained on the basis of a non-equilibrium asymmetric arrangement of the PDA at the electrode due to retarded rotation, based on the hypothesis of sup er viscos it y of t he nearelectr ode la yer . The formation of the superviscous layer has been explained by the near-electrode structuring of the polarized DMSO molecules, caused, in particular, by the strong electric field. From the higher yield of A > B, i.e. R = A/B > 1, the atom C1 must be directed towards the electrode. Then, a greater negative charge is induced on the carbon atom C5 of PDA, which is most distant from the electrode surface (according to our estimates the difference Δ = -0.051 ÷ 0.079 ), and it is protonated at a higher rate. T he eff ect ive near-electrode orientations of the PDA, angle φ eff of the PDA's axis C1-C5 with electrode plane, have been found , Fig. ; it also represents the orientation of the starting molecule, estimated from the dipole moment . The value of this angle φ eff = arctg [(R -1)/2] increases in the series of X-substituents -OCOCH 3 < -OCH 3 < -OH, i.e., as its polarity increases and its size decreases (greater attraction of the substrate molecule to the electrode surface). A kinetic analysis performed gives for the rate constant of the PDA reorientation into an equilibrium position k r < 1×10 -6 s -1 , i.e. 3-5 orders of magnitude lower than the rotation frequencies of molecules in common liquids . Therefore, the above reaction Scheme 3 should be supplemented with the stage of the slow rearrangement (r) of the PDA, i.e. in fact, we have a process ederp vs. e v de v p for the HOMEC electrolysis (e v are the "volume" ET-stages). Thus, Stal Mairanovskii´s idea about "inheritance of the orientation", "carry-over effect" [8, en, p.219] does occur, it is first confirmed by the direct experiment; however, in contrast to all previous studies, this is here about fr ee, specifically no n-a ds or b ed s p ecies . Another notable difference was the predominant formation of the thermodynamically less favorable cis-forms in the case of direct electrolysis, for both isomers A, B, in cont r as t t o H OM EC (see C/D -rates, Table , and Supplement).