Abstract
The application of high-pressure kinetics as a tool to investigate the detailed mechanism of catalysis of a reaction is demonstrated. Activation volumes have been determined for the Diels-Alder addition of 2, 3-dimethylbutadiene to n-butyl acrylate, both uncatalyzed and catalyzed with AICI3. Also, partial molal volumes of reactants and products have been measured. From these data it is shown that the volume profile along the reaction coordinate is similar for both the catalyzed and uncatalyzed reactions. Further, both reactions proceed by a concerted one-step mechanism through a compact transition state with maximum accumulation of double bonds. Thus, the role of the Lewis acid in catalyzing the reaction is not to alter the mechanism but rather to render the dienophile more reactive by making it more electron deficient. © 1972, American Chemical Society. All rights reserved.
Recommended Citation
B. E. Poling and C. A. Eckert, "A Study Of Homogeneous Catalysis By High-Pressure Kinetics. The Mechanism Of Catalysis Of A Diels—Alder Reaction," Industrial and Engineering Chemistry Fundamentals, vol. 11, no. 4, pp. 451 - 457, American Chemical Society, Nov 1972.
The definitive version is available at https://doi.org/10.1021/i160044a004
Department(s)
Chemical and Biochemical Engineering
International Standard Serial Number (ISSN)
0196-4313
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2023 American Chemical Society, All rights reserved.
Publication Date
01 Nov 1972
