Reactions of N1‐Methyl‐4‐nitro‐2,1,3‐benzoselenadiazolium Tetrafluoroborate with Aliphatic and Cyclic Amines in Acetonitrile: Kinetic and Structure‐Reactivity Correlations

• Published in: International journal of chemical kinetics Vol. 49; no. 8; pp. 576 - 583
• Main Authors: Salah, S. Ben, Boubaker, T., Goumont, R.
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc 01-08-2017
• Subjects: Acetonitrile; Aliphatic amines; Amines; Cations; Constants; Kinetics; Mathematical analysis; Morpholine; Piperidine; Rate constants; Reliability; Spectroscopic analysis; Unity
• ISSN: 0538-8066; 1097-4601
• DOI: 10.1002/kin.21096

ABSTRACT
The nucleophilic addition reactions of N1‐methyl‐4‐nitro‐2,1,3‐benzoselenadiazolium tetrafluoroborate 1 with aliphatic amines 2a–c (diethylamine 2a, dipropylamine 2b, and allylamine 2c) have been kinetically studied by UV–vis spectroscopy in acetonitrile solution at 20°C. The kinetic data have been analyzed, using the Mayr equation, allowing the quantification of the electrophilicity parameter (E) value of benzoselenadiazolium cation 1 (E = −14.72). The reliability of parameter E has been reasonably verified by comparison of calculated and experimental second‐order rate constants for the reactions of cation 1 with other amines 2d–f (pyrrolidine 2d, piperidine 2e, and morpholine 2f) under the same conditions as those of the amines 2a–c. A linear Brönsted plot (R2 = 0.9945) with a βnuc value of 0.55 has been obtained for the reactions of 1 with the secondary amines employed in the present work. Interestingly, satisfactory correlation between the log values of measured and calculated rate constants with a slope very close to unity has been obtained and discussed.