Versatile synthesis of cadalene and iso-cadalene from himachalene mixtures: Evidence and application of unprecedented rearrangements |
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Affiliation: | 1. Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Akademicheskii pr. 4, Tomsk, 634021, Russia;2. A.A. Trofimuk Institute of Petroleum Geology and Geophysics, Siberian Branch of the Russian Academy of Sciences, pr. Akademika Koptyuga 3, Novosibirsk, 630090, Russia;3. Novosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090, Russia |
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Abstract: | From a mixture of α-, β- and γ-himachalenes extracted from waste wood of Atlas cedar (Cedrus atlantica), cadalene (1,6-dimethyl-4-isopropylnaphthalene) and iso-cadalene (1,6-dimethyl-3-isopropylnaphthalene) were produced in two steps with up to 71% ± 5% yield through the ar-himachalene intermediate using I2 and/or AlCl3 as reagents. The selectivity is shown to sharply depend on the operating conditions: while I2/AlCl3 in dichloromethane promotes the formation of cadalene, the formation of iso-cadalene is favored in the presence of AlCl3 in cyclohexane. The bicyclic aromatic compounds were thus obtained through unique rearrangements involving sequential CC bond cleavage/formation and hydride transfer processes. In the absence of AlCl3 or I2, dihydrocurcumene was also found to be formed with up to 70% selectivity. A tentative mechanism is proposed and discussed. |
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Keywords: | Aromatic reactivity Cadalenes Dihydrocurcumene Himachalenes Rearrangements |
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