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Synthetic and photochemical studies of substituted 1-acyl-7-nitroindolines

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Abstract

A previous study of substituent effects on the photocleavage of 1-acyl-7-nitroindolines has been extended to examine the effects of electron-donating and electron-withdrawing substituents. 1-Acetyl-4,5-methylenedioxy-7-nitroindoline 7 was inert to 350 nm irradiation, reinforcing an earlier finding that excessive electron-donation by substituents can divert the excited state into non-productive pathways. By contrast, the 1-acetyl-5,7-dinitro- and 1-acetyl-4-methoxy-5,7-dinitroindolines 8 and 9 respectively both showed improved photolysis efficiency in aqueous solution compared to the 1-acyl-4-methoxy-7-nitro compound 2. Unlike 2, both 8 and 9 gave mixed photoproducts, the corresponding dinitroindolines and the 5-nitro-7-nitrosoindoles. These results are interpreted in terms of a previous mechanistic study. Investigation of the 4-methoxy-5,7-dinitroindoline conjugate of l-glutamate 18 showed that the stoichiometry of glutamate release upon photolysis was only 65-77% of the theoretical value, suggesting that photolysis of these dinitro compounds may involve pathways other than the clean photolysis previously observed for mono-nitro compounds such as 2.

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Authors and Affiliations

  1. National Institute for Medical Research, The Ridgeway, Mill Hill, London, UK, NW7 1AA

    George Papageorgiou, David Ogden & John E. T. Corrie

  2. MRC Biomedical NMR Centre, The Ridgeway, Mill Hill, London, UK, NW7 1AA

    Geoff Kelly

Authors
  1. George Papageorgiou
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  2. David Ogden
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  3. Geoff Kelly
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  4. John E. T. Corrie
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Correspondence to John E. T. Corrie.

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Papageorgiou, G., Ogden, D., Kelly, G. et al. Synthetic and photochemical studies of substituted 1-acyl-7-nitroindolines. Photochem Photobiol Sci 4, 887–896 (2005). https://doi.org/10.1039/b508756b

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