Isomerization of 1-butene on high-temperature-chlorinated alumina.

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概要

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• Regarding aluminas chlorinated at 973–1223 K, which have only a Lewis acidic character without hydroxyl groups and basic sites, the IR spectra of the adsorbed 1-butene were measured and the isomerization of 1-butene and <I>cis</I>-2-butene was performed at 273–323 K. The obtained results were compared with those for aluminas dehydrated at the same temperatures. The IR spectra of the adsorbed 1-butene well resembled that of <I>cis</I>-2-butene, including the absence of peaks due to double-bond and π-allyl carbanion species, observed even after outgassing at 473 K. During isomerization at 273 K, the initial isomerization reaction rates and cis/trans ratios were greater than those for dehydrated alumina. The ratio decreased rapidly with increasing reaction temperature. The specific reaction rates and the ratio were independent of the chlorination temperature. In the isomerization of <I>cis</I>-2-butene the most thermodynamically unstable molecule, 1-butene, was formed preferentially. The obtained results could be interpreted by an isomerization mechanism through a doubly bonded intermediate, i.e., the allylic butenyl cation.

• 公益社団法人 日本化学会の論文

著者

• Ayame Akimi

  Department Of Applied Chemistry Muroran Institute Of Technology

• Sawada Goro

  Department of Industrial Chemistry, Muroran Institute of Technology

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