Reactivities of Stable Rotamers. XXXIII. Addition of Positive Bromine Compounds to the Olefinic Moiety of 1-(9-Fluorenyl)-2-(1-methylethenyl)naphthalene Rotamers and Facile Benzene Ring Cleavage in One of the Intermediates from the <i>sp</i>-Form

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  • Michinori Oki
    Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700
  • Kiyoka Maeda
    Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700
  • Tadashi Akinaga
    Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700
  • Yasukazu Kataoka
    Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700
  • Shinji Toyota
    Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700

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<jats:title>Abstract</jats:title> <jats:p>Addition of positive bromine compounds to the title olefins was carried out with use of N-bromosuccinimide–water and t-butyl hypobromite and the results are compared with the case of bromine addition. In the case of the ap-isomer, the reactions reported here all produce bromo-olefins in addition to an addition product, in contrast to the case of bromine which gives only an addition product. The sp-isomer afforded the same products as was observed for the bromine-addition but with different proportions of the products. The anionic species of more proton affinity and consequently of less affinity toward carbocations caused a decrease in formation of the addition product and an increase in formation of bromo-olefins in the case of the ap-isomer. The ratios of products, bromo-olefins to a cyclized compound, were affected by the anionic species in the case of sp-isomer: Both N-bromosuccinimide–water and t-butyl hypobromite yielded about the same amounts of the two olefins, but the yields of the cyclized compound varied significantly. The results are not explained in a straightforward manner. Probably solvent effects are important. In addition, the reaction of the sp-form with N-bromosuccinimide in tetrahydrofuran-water afforded (7R*,7aS*,12bS*)-7-bromomethyl-8-[(E)-bromomethylene]-7-methyl-7a-[(Z)-3-oxo-1-propenyl]-7,7a,8,12b-tetrahydrobenzo[5,6]pentaleno[1,2-a]naphthalene, a compound which is derived by cleavage of a benzene ring. The structural features of the last compound are also discussed.</jats:p>

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