Abstract
The nucleophilic photosubstitution of alkoxy and other leaving groups in nitrophenyl ethers is a potentially useful reaction in photoaffinity labelling experiments. A mechanistic study of the photoreactions of several nitrophenyl ethers with different amines and hydroxide ion is presented. Three different mechanistic pathways have been identified for the photosubstitutions of 4-nitroveratrole. The photoreaction with hydroxide ion takes place in meta position with respect to thg nitro group by a mechanism involving the excited triplet state (SN23Ar*). The photosubstitution with n-hexylamine occurs mainly in meta position through the singlet excited state (SN21Ar*). Finally, the photosubstitution with piperidine occurs in para position and the mechanism involves an electron transfer from the amine to the excited triplet state. The different regioselectivities observed with different amines depend upon the ionization potential of the amines.
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© 1989 Kluwer Academic Publishers
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Marquet, J., Moreno-Mañas, M. (1989). Nucleophilic Aromatic Photo Substitutions on Nitrophenyl Ethers. A New Photoaffinity Labelling Technique?. In: Nielsen, P.E. (eds) Photochemical Probes in Biochemistry. NATO ASI Series, vol 272. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0925-0_2
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DOI: https://doi.org/10.1007/978-94-009-0925-0_2
Publisher Name: Springer, Dordrecht
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