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Temperature-sensitive photochemical aromatic substitution on 4-nitroanisole

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Abstract

A temperature-sensitive photochemical nucleophilic aromatic substitution on 4-nitroanisole by a hydroxide ion in homogeneous solutions, in a two-phase system under phase-transfer catalysis conditions, and in the microwave field is reported. It was found that reaction regioselectivity dramatically changes with temperature in the region of −20 to 196 °C. The quantum yield of the 4-methoxyphenol formation was found to be temperature independent, in contrast to that of the 4-nitrophenol formation, suggesting that there is a temperature dependent process occurring after the partitioning between replacement of the nitro group and the methoxy group has taken place. The reaction was also investigated by using quantum chemical calculations. A technique for microwave-assisted photochemical synthesis is proposed as an efficient and practical tool for organic synthesis.

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Authors and Affiliations

  1. Department of Organic Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37, Brno, Czech Republic

    Petr Klán, Radovan Růžička, Dominik Heger & Jaromír Literák

  2. National Centre for Biomolecular Research, Faculty of Science, Masaryk University, Kotlarska 2, 611 37, Brno, Czech Republic

    Petr Kulhánek

  3. Laboratoire des Réactions Sélectives sur Supports, ICMMO, Université Paris-Sud, CNRS, UMR 8615, Bâtiment 410, 91405, Orsay Cedex, France

    André Loupy

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  1. Petr Klán
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Correspondence to Petr Klán.

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Klán, P., Růžička, R., Heger, D. et al. Temperature-sensitive photochemical aromatic substitution on 4-nitroanisole. Photochem Photobiol Sci 1, 1012–1016 (2002). https://doi.org/10.1039/b209010d

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