13659-02-4Relevant academic research and scientific papers
Neighboring group participation in the gas phase. The homogeneous elimination kinetics of 5-(N-phenylamino)-1-pentyl acetate and 5-(N-methyl-N-phenylamino)-1-pentyl acetate
Chuchani, Gabriel,Al-Awadi, Nouria,Dominguez, Rosa M.,Kaul, Kamini
, p. 180 - 186 (2007/10/03)
The elimination kinetics of the title compounds were determined over the temperature range 370-420°C and pressure range of 36-91 Torr (1 Torr = 133.3 Pa). The reactions carried out in seasoned vessels with the free radical suppressor toluene always present are homogeneous, unimolecular and obey a first-order rate law. The overall rate coefficient is expressed by the following Arrhenius equations: for 5-(N-phenylamino)-1-pentyl acetate, log k1 (s-1) = (13.56 ± 0.19) - (211.8 ± 2.2) kJ mol-1 (2.303RT)-1 and for 5-(N-methyl-N-phenylamino)-1-pentyl acetate, log k1 (s-1) = (12.29 ± 0.41) - (182.9 ± 5.2) kJ mol-1 (2.303RT)-1. The formation of N-phenylpiperidine in both reactions suggests the anchimeric assistance of the PhNH and Ph(CH3)N groups for a backside displacement. An intimate ion-pair type of mechanism is assumed in the pyrolytic elimination of these phenylaminoalkyl acetates. Copyright
