Substituent effects in the gas-phase pyrolysis of 4-(N-arylamino)-1-butyl acetate and 5-(N-arylamino)1-pentyl acetate

A kinetic study of the gas-phase pyrolysis of 4- and 5-(N-arylamino)-1-buty l and -1-pentyl acetate was made. Each ester was pyrolysed at five or six d ifferent temperatures and over a temperature range not less than 50 degrees C. These reactions were homogeneous and unimolecular. The reactivities of t hese compounds were compared with those of the parent compounds 4- and 5-(N -phenyl)-1-butyl and -1-pentyl acetate and with each other. The products of the decomposition reaction of these compounds suggest an anchimeric assist ance of the amino substituent for a trans elimination, indicating that an i on-pair type of mechanism may be operating during the process of eliminatio n. Copyright (C) 2000 John Wiley & Sons, Ltd.