Abstract
Thermal Rearrangement of 2-3.2.0] hepta-3,6-Diene-6,7-Dicarbonitrile8 1–3 to their 4,5-Dicarbonitrile Isomers 4–6 Takes Place at 110–140 °C in Yields of 82–84%. the Reactions Are First Order with Rates Almost Independent of the Polarity of the Solvent. Activation Parameters (ΔH‡ = 120–140 KJ Mol−1 and ΔS‡ ≈ 0 J K−1 Mol−1) Are in Agreement with a Concerted Symmetry-Allowed Antarafacial-Antarafacial Cope Rearrangement. Compounds 1–3 Rearrange Photochemically Via Cleavage of the C-1-S Bond to the 1,7-Dicarbonitrile Isomers 7–9. Isomer 9 Rearranges Further on Prolonged Irradiation to Give 10. a Tentative Mechanism for This Rearrangement is Given. © 1982, American Chemical Society. All Rights Reserved.
Recommended Citation
Hall, R. H., den Hertog, H. J., & Reinhoudt, D. N. (1982). 2-Thiabicyclo[3.2.0]hepta-3,6-Dienes. 2. Thermal and Photochemical Isomerization of 2-Thiabicyclo[3.2.0]hepta-3,6-Dienes. an Example of the Antarafacial-Antarafacial Cope Rearrangement. Journal of Organic Chemistry, 47(6), pp. 972-977. American Chemical Society.
The definitive version is available at https://doi.org/10.1021/jo00345a015
Department(s)
Business and Information Technology
International Standard Serial Number (ISSN)
1520-6904; 0022-3263
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2023 American Chemical Society, All rights reserved.
Publication Date
01 Jan 1982
