591235-69-7Relevant academic research and scientific papers
Nucleophilic substitution reactions of α-chloroacetanilides with benzylamines in dimethyl sulfoxide
Lee, Ki Sun,Adhikary, Keshab Kumar,Lee, Hai Whang,Lee, Bon-Su,Lee, Ikchoon
, p. 1989 - 1994 (2003)
Kinetic studies of the reactions of α-chloroacetanilides (YC6H4NRC(=O)CH2Cl; R = H (5) and CH3 (6)) with benzylamines (NH2CH2C6H4X) were carried out in dimethyl sulfoxide at 55.0°C. The Bronsted βX values were in the range from 0.6 to 0.9 and cross-interaction constants ρXY were positive: ρXY = +0.21 and +0.18 for 5 and 6, respectively. The rates were faster with 6 than with 5 and inverse secondary kinetic isotope effects involving deuterated benzylamine (ND2CH2C6H4X) nucleophiles, kH/kD ±, is proposed. In this mechanism, a prior carbonyl addition to T± is followed by a bridged type transition state to expel the chloride. An enolate-like transition state in which the developing negative charge on Cα delocalizes toward the carbonyl group (nC→π*C=O interaction) is not feasible for the present series of reactions due to a stronger charge transfer involving the lone pair on the anilino nitrogen (nAN→π*C=O interaction).
