AbstractThe quantum‐chemical PCILO method has been used to perform a conformational analysis of the 1‐[2‐(2‐methoxyphenylcarbamoyloxy)ethyl]piperidine(B)and its cation(BH⊕)which belong to a group of phenylcarbamates with considerable local anesthetic activity. ForBthe most stable conformation has a gauche arrangement of the O‐C‐C‐N fragment. ForBH⊕ the most stable conformer is stabilized by an intramolecular hydrogen bond of the N⊕‐H…︁O=C type. Using the PCILO and “double zeta” ab initio methods the protonation energies were calculated. The gross atomic charges resulting from the “double zeta” ab initio calculations forBandBH⊕ were compared with the results of the