T. P. Lockhart, C. Mallon, R. Bergman
Aug 27, 1980
Citations
0
Influential Citations
131
Citations
Quality indicators
Journal
Journal of the American Chemical Society
Abstract
In this paper, a detailed study of the thermolysis of (Z)-4,5-diethynyl-4-octene (4) is presented. This reaction gives high yields of products formed by rearrangement and intramolecular and intermolecular trapping of the intermediate 1,4-dehydrobenzene 5. The kinetics of the solution pyrolysis of 4 in the presence and absence of trapping agent establish that the 1,4-dehydrobenzene is a discrete intermediate on the pathway leading to products. By following this reaction in the probe of an NMR spectrometer at high temperature, CIDNP in a 1,4-dehydrobenzene reaction was observed for the first time. This observation, along with kinetic and chemical trapping evidence, indicates the subsequent formation of two additional intermediates on the pathway to products. The observation of CIDNP, coupled with the reactivity exhibited by 5 and the other two intermediates, implicate a biradical description of these molecules.