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Competing processes in the photochemistry of picolines and their N-methyl salts: photoinduced charge transfer, phototransposition and photohydration

Research on Chemical Intermediates volume 43, pages 859–871 (2017)Cite this article

Abstract

Photochemical reactivity of a series of picolines and their N-methylated salts has been investigated by preparative irradiations and UV–vis spectroscopy. Understanding competing photochemical processes and knowledge of their relative efficiencies is important in the application of pyridines as photocages or in the synthesis of complex polycycles. Contrary to previous reports for the gas phase, picolines are not reactive in the phototransposition, presumably due to protonation of the pyridine nitrogen in the excited state. Deuterium exchange was observed upon irradiation in CD3CN–D2O, but it was rationalized by photoionization and radical formation. On the other hand, N-methylated picoline salts are not protonated upon excitation. They undergo photohydration and phototransposition (Φ R = 0.01–0.06). Upon irradiation of iodides, azabicyclic [3.1.0] hydration products were obtained. A difference in product distribution was observed between iodides and perchlorates, due to photoelimination of perchloric acid leading to the thermal aziridine ring opening. Moreover, excitation of iodide derivatives gives rise to change transfer transition forming iodide radicals that eventually give I3 − with the quantum efficiency Φ R = 0.015–0.02.

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Acknowledgments

These materials are based on work financed by the Croatian Ministry of Science Education and Sports (MZOS) and the Croatian Science Foundation (HRZZ Grants 02.05/25 and IP-2014-09-6312).

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  1. Department of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička cesta 54, 10 000, Zagreb, Croatia

    Vesna Blažek Bregović & Nikola Basarić

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  1. Vesna Blažek Bregović
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  2. Nikola Basarić
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Correspondence to Nikola Basarić.

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Blažek Bregović, V., Basarić, N. Competing processes in the photochemistry of picolines and their N-methyl salts: photoinduced charge transfer, phototransposition and photohydration. Res Chem Intermed 43, 859–871 (2017). https://doi.org/10.1007/s11164-016-2669-6

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  • DOI: https://doi.org/10.1007/s11164-016-2669-6

Keywords

  • Pyridine
  • Pyridinium salt
  • Excited state proton transfer
  • Excited state charge transfer
  • Phototransposition
  • Photohydration