Mechanistic and Kinetic Insights into the Thermally Induced Rearrangement of a-Pinene.

[摘要]：The thermal rearrangement of a-pinene (1) is interesting from mechanistic as well as kinetic point of view. Carrier gas pyrolysis with 1 and its acyclic isomers ocimene (2) and alloocimene (3) were performed to investigate the thermal network of these hydrocarbons. Kinetic anal. of the major reaction steps allows for a deeper insight in the reaction mechanism. Thus it was possible to explain the racemization of 1, the formation of racemic limonene (4), and the absence of the primary pyrolysis product 2 in the reaction mixt. resulting from thermal rearrangement of 1. Results supported the conclusion that the reactions starting with 1 involve biradical transition states.

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