| Autor: |
Mittal K; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States., Pham AV; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States., Davis AG; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States., Richardson AD; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States., De Hoe C; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States., Dean RT; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States., Baird V; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States., McDonald AR; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States., Frantz DK; Department of Chemistry and Biochemistry, California Polytechnic State University, 1 Grand Avenue, San Luis Obispo, California 93407, United States. |
| Abstrakt: |
At elevated temperatures, a strained, cyclic meta -quaterphenylene acetylene undergoes an intramolecular cyclization reaction to form benz[ e ]indeno[1,2,3- hi ]acephenanthrylene. This reaction represents an example of a Diels-Alder reaction at the 2-, 1-, 1'-, and 2'-positions of a biphenyl derivative, a region analogous to the bay regions of perylene and other periacenes. The reaction proceeds cleanly with high conversion. Kinetics studies of a methylated derivative reveal that the Δ G ‡ for the reaction is ∼40-41 kcal/mol, and computational models predict a similar value of G rel for the transition state of a concerted [4 + 2]-cycloaddition. |
