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      One-step selective hydroxylation of benzene to phenol with hydrogen peroxide catalysed by copper complexes incorporated into mesoporous silica–alumina†

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      Chemical Science
      Royal Society of Chemistry

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          Abstract

          One-step hydroxylation of benzene with hydrogen peroxide to produce phenol catalyzed by a copper( ii) complex.

          Abstract

          Benzene was hydroxylated with hydrogen peroxide (H 2O 2) in the presence of catalytic amounts of copper complexes in acetone to yield phenol at 298 K. At higher temperatures, phenol was further hydroxylated with H 2O 2 by catalysis of copper complexes to yield p-benzoquinone. The kinetic study revealed that the rate was proportional to concentrations of benzene and H 2O 2, but to the square root of the concentration of a copper( ii) complex ([Cu(tmpa)] 2+: tmpa = tris(2-pyridylmethyl)amine). The addition of a spin trapping reagent resulted in formation of a spin adduct of hydroperoxyl radical (HO 2˙), as observed by EPR spectroscopy, inhibiting phenol formation. HO 2˙ produced by the reaction of [Cu(tmpa)] 2+ with H 2O 2 acts as a chain carrier for the radical chain reactions for formation of phenol. When [Cu(tmpa)] 2+ was incorporated into mesoporous silica–alumina (Al-MCM-41) by a cation exchange reaction, the selectivity for production of phenol was much enhanced by prevention of hydroxylation of phenol, which was not adsorbed to Al-MCM-41. The high durability with a turnover number of 4320 for the hydroxylation of benzene to phenol with H 2O 2 was achieved using [Cu(tmpa)] 2+ incorporated into Al-MCM-41 as an efficient and selective catalyst.

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          Author and article information

          Journal
          Chem Sci
          Chem Sci
          Chemical Science
          Royal Society of Chemistry
          2041-6520
          2041-6539
          1 April 2016
          5 January 2016
          : 7
          : 4
          : 2856-2863
          Affiliations
          [a ] Department of Material and Life Science , Graduate School of Engineering , Osaka University , ALCA and SENTAN , Japan Science and Technology (JST) , Suita , Osaka 565-0871 , Japan . Email: fukuzumi@ 123456chem.eng.osaka-u.ac.jp
          [b ] Department of Chemistry , The Johns Hopkins University , Baltimore , Maryland 21218 , USA . Email: karlin@ 123456jhu.edu
          [c ] Department of Chemistry and Nano Science , Ewha Womans University , Seoul 120-750 , Korea
          [d ] Faculty of Science and Engineering , Meijo University , ALCA and SENTAN , Japan Science and Technology Agency (JST) , Nagoya , Aichi 468-0073 , Japan
          Article
          c5sc04312c
          10.1039/c5sc04312c
          4951108
          27453774
          242f27c0-a643-49db-b49e-d283ae518fc0
          This journal is © The Royal Society of Chemistry 2016

          This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0)

          History
          : 12 November 2015
          : 5 January 2016
          Categories
          Chemistry

          Notes

          †Electronic supplementary information (ESI) available: Cyclic voltammogram (Fig. S1), time profiles of phenol, p-benzoquinone, H 2O 2, spin or benzene (Fig. S2–S5 and S9 and S10), DFT results (Fig. S6 and Tables S1 and S2), UV-Vis absorption spectra (Fig. S7) and UV-Vis DRS (Fig. S8). See DOI: 10.1039/c5sc04312c


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