The α-Effect in Reactions of sp-Hybridized Carbon Atom:  Michael-Type Reactions of 1-Aryl-2-propyn-1-ones with Primary Amines

• Published in: Journal of organic chemistry Vol. 70; no. 19; pp. 7530 - 7536
• Main Authors: Um, Ik-Hwan, Lee, Eun-Ju, Seok, Jin-Ah, Kim, Kyung-Hee
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 16.09.2005
• Subjects: Chemistry; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms; Michael addition; Substituent effect; Acetylenic compound; Ketone; Kinetic isotope effect; Alpha effect; Aromatic compound; Alkalinity; Kinetics; Rate constant; Hydrazine; Primary amine; Hydrogen bond; Nucleophile
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo050624t

Second-order rate constants (k N) have been measured for the Michael-type reaction of 1-(X-substituted phenyl)-2-propyn-1-ones (2a−f) with a series of primary amines in H2O at 25.0 ± 0.1 °C. A linear Brønsted-type plot with a small βnuc value (βnuc = 0.30) has been obtained for the reactions of 1-phenyl-2-propyn-1-one (2c) with non-α-nucleophile amines. Hydrazine is more reactive than other primary amines of similar basicity (e.g., glycylglycine and glycine ethyl ester) and results in a positive deviation from the linear Brønsted-type plot. The reactions of 2a−f with hydrazine exhibit a linear Hammett plot, while those with non-α-nucleophile amines give linear Yukawa−Tsuno plots, indicating that the electronic nature of the substituent X does not affect the reaction mechanism. The α-effect increases as the substituent X in the phenyl ring of 2a−f becomes a stronger electron-donating group. However, the magnitude of the α-effect for the reactions of 2a−f is small (e.g., k N hydrazine/k N glycylglycine = 4.6−13) regardless of the electronic nature of the substituent X. The small βnuc has been suggested to be responsible for the small α-effect. A solvent kinetic isotope effect (e.g., k N H 2 O/k N D 2 O = 1.86) was observed for the reaction with hydrazine but absent for the reactions with non-α-nucleophile amines. The reactions with hydrazine and other primary amines have been suggested to proceed through a five-membered intramolecular H-bonding structure VI and a six-membered intermolecular H-bonding structure VII, respectively. The transition state modeled on VI can account for the substituent dependent α-effect and the difference in the solvent kinetic isotope effect exhibited by the reactions with hydrazine and other primary amines. It has been proposed that the βnuc value is more important than the hybridization type of the reaction site to determine the magnitude of the α-effect.