Incorporation of an allene unit into 1,4-dihydronaphthalene: generation of 1,2-benzo-1,4,5-cycloheptatriene and its dimerization |
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Authors: | Akin Azizoglu Onur Demirkol Y. Kemal Yildiz |
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Affiliation: | a Department of Chemistry, Balikesir University, Balikesir TR-10145, Turkey b Department of Chemistry, Nigde University, Nigde TR-51200, Turkey |
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Abstract: | 1-Bromo-1-fluoro-[1a,2,7,7a]-tetrahydro-1H-cyclopropa[b]naphthalene (19) has been prepared by the addition of bromofluorocarbene to 1,4-dihydronaphthalene (18). Treatment of a solution of 19 in dry ether with MeLi afforded the tricyclic hydrocarbon 17, resulting from the intramolecular C-H insertion of carbene 16, and two dimerization products, the head-to-head 20 and head-to-tail 21 allene dimers, confirming the formation of title cycloallene 15 as a reactive intermediate. B3LYP/6-31G(d) calculation predicts the activation barriers for insertion product 17 and allene product 15 as 3.70 and 9.52 kcal/mol, respectively. This prediction was in good agreement with our experimental results. |
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Keywords: | Cyclic allenes Carbenes Rearrangements DFT calculations |
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