Thermal decarbonylation of tropone.

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概要

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• Thermal reaction of tropone has been studied at temperatures ranging from 420 to 490 °C and at residence times ranging from 1.5 to 6.9 s using a conventional flow apparatus. Tropone undergoes first-order unimolecular decarbonylation. The value of kinetic parameters for this reaction are evaluated as being: <I>A</I>=10<SUP>14.2</SUP>s<SUP>−1</SUP>, <I>E</I><SUB>a</SUB>=54.1 kcal mol<SUP>−1</SUP>, <I>ΔS</I><SUP>\neweq</SUP>=2.8 eu, <I>ΔH</I><SUP>\neweq</SUP>=52.6 kcal mol<SUP>−1</SUP>, and <I>ΔG</I><SUP>\neweq</SUP>=50.6 kcal mol<SUP>−1</SUP>. These values indicate that the decarbonylation takes place by one-step concerted mechanism <I>via</I> a norcaradienone-like transition complex. The latter complex is characterized by a partial transannular C<SUB>2</SUB>–C<SUB>7</SUB> bond formation and concerted elongation of C<SUB>1</SUB>–C<SUB>2</SUB> and C<SUB>1</SUB>–C<SUB>7</SUB> bonds in tropone. The proposed transition complex is in conformity with reported thermal behavior of 1,3,5-cycloheptatriene as well as with molecular orbital symmetry theory.

著者

• OKAYAMA Kiyoaki

  Department of Applied Biology, Faculty of Textile Science, Kyoto Institute of Technology

• Nakazawa Tomoo

  Department Of Chemistry Yamanashi Medical College

• Mukai Toshio

  Department of Chemistry, Faculty of Science, Tohoku University

• Amano Akira

  Department of Applied Chemistry, Faculty of Engineering, Tohoku University

• Mukai Toshio

  Department of Chemistry, Faculty of Science Tohoku University

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