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Effects of 4,5-dimethoxy groups on the time-resolved photoconversion of 2-nitrobenzyl alcohols and 2-nitrobenzaldehyde into nitroso derivatives

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Abstract

The photoinduced conversion of the aci-nitro in the nitroso form was studied with four compounds containing the o-nitrobenzyl moiety in solution at ambient temperature using time-resolved UV-vis spectroscopy. For 4,5-dimethoxy-2-nitrobenzyl alcohol (2) and 4,5-methylenedioxy-2-nitrobenzyl alcohol (3) the absorption spectra are red-shifted and, in contrast to the parent 2-nitrobenzyl alcohol (1), a triplet state with CT character was detected after the 308 nm laser pulse. The other photochemical properties of 1–3 are similar. The aci-nitro form of 1–3 in acetonitrile or ethanol is quenched by water, the rate constant is (0.3–1.7) × 105 M−1 s−1. A CT triplet state and the nitroso product but no aci-nitro form were observed for 4,5-methylenedioxy-2-nitrobenzaldehyde (4). The conversion of the aci-nitro into the nitroso monomer and eventual dimer formation were studied by FTIR spectroscopy. The common features and specific differences in the photoreaction mechanisms of 1–4 are discussed.

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References

  1. H. A. Morrison, The Photochemistry of the Nitro and Nitroso Groups, in The Chemistry of the Nitro and Nitroso Groups, ed. H. Feuer, Wiley, New York, 1969, pp. 165–213.

    Google Scholar 

  2. D. Döpp, Photochemical reactivity of the nitro group, CRC Handbook of Photochemistry and Photobiology, ed. W. M. Horspool and P.-S. Song, CRC Press, Boca Raton, FL, 1995, pp. 1019–1062.

  3. J. A. McCray and D. R. Trentham, Properties and uses of photoreactive caged compounds, Annu. Rev. Biophys. Biomol. Struct., 1989, 18, 239–270.

    Article  CAS  Google Scholar 

  4. M. V. George and J. C. Scaiano, Photochemistry of o-nitrobenzaldehyde and related studies, J. Phys. Chem., 1980, 84, 492–495.

    Article  CAS  Google Scholar 

  5. S. Abbruzzetti, M. Carcelli, D. Rogolino and C. Viappiani, Deprotonation yields, p Ka, and aci-nitro decay rates in some substituted o-nitrobenzaldehydes, Photochem. Photobiol. Sci., 2003, 2, 796–800.

    Article  CAS  Google Scholar 

  6. H. Schupp, W. K. Wong and W. Schnabel, Mechanistic studies of the photorearrangement of o-nitrobenzyl esters, J. Photochem., 1987, 36, 85–97.

    Article  CAS  Google Scholar 

  7. Q. Q. Zhu, W. Schnabel and H. Schupp, Formation and decay of nitronic acid in the photorearrangement of o-nitrobenzyl esters, J. Photochem., 1987, 39, 317–332.

    Article  CAS  Google Scholar 

  8. T. Milburn, N. Matsubara, A. P. Billington, J. B. Udgaonkar, J. W. Walker, B. K. Carpenter, W. W. Webb, J. Marque, W. Denk, J. A. McCray and G. P. Hess, Synthesis, photochemistry, and biological activity of a caged photoliable actylcholine receptor ligand, Biochemistry, 1989, 28, 49–55.

    Article  CAS  Google Scholar 

  9. L. Niu, K. R. Gee, K. Schaper and G. P. Hess, Synthesis and photochemical properties of a kainate precursor and activation of kainate and AMPA receptor channels on a microsecond time scale, Biochemistry, 1996, 35, 2030–2036.

    Article  CAS  Google Scholar 

  10. K. R. Gee, L. Niu, K. Schaper, V. Jayaraman and G. P. Hess, Synthesis and photochemistry of a photoliable precursor of N-methyl-d-asparate (NMDA) that is photolyzed in the microsecond time region and is suitable for chemical kinetic investigations of the NMDA receptor, Biochemistry, 1999, 38, 3140–3147.

    Article  CAS  Google Scholar 

  11. C. Grewer, S. A. M. Mobarekeh, N. Watzke, T. Rauen and K. Schaper, Substrate translocation kinetics of excitatory amino acid carrier 1 probed with laser-pulse photolysis of a new photoliable precursor ofd-asparatic acid, Biochemistry, 2001, 40, 232–240.

    Article  CAS  Google Scholar 

  12. S. Walbert, W. Pfleiderer and U. E. Steiner, Photoliable protecting groups for nucleosides: mechanistic studies of the 2-(2-nitrophenyl)ethyl group, Helv. Chim. Acta, 2001, 84, 1601–1611.

    Article  CAS  Google Scholar 

  13. K. Schaper, S. A. M. Mobarekeh and C. Grewer, Synthesis and photophysical characterization of a new, highly hydrophilic caging group, Eur. J. Org. Chem., 2002, 1037–1046.

    Google Scholar 

  14. A. Barth, K. Hauser, W. Mäntele, J. E. T. Corrie, D. R. Trentham, Photochemical release of ATP from “caged ATP” studied by time-resolved infrared spectroscopy, J. Am. Chem. Soc., 1995, 117, 10311–10316

    Article  CAS  Google Scholar 

  15. A. Barth, J. E. T. Corrie, M. J. Gradwell, Y. Maeda, W. Mäntele, T. Meier and D. R. Trentham, Time-resolved infrared spectroscopy of intermediates and products from photolysis of 1-(2-nitrophenyl)ethyl phosphates: reaction of the 2-nitrosoacetophenone byproduct with thiols, J. Am. Chem. Soc., 1997, 119, 4149–4159.

    Article  CAS  Google Scholar 

  16. I. R. Dunkin, J. Gebicki, M. Kiszka and D. Sanin-Leira, Phototautomerism of o-nitrobenzyl compounds: o-quinoid aci-nitro species studied by matrix isolation and DFT calculations, J. Chem. Soc., Perkin Trans. 2, 2001, 1414–1425.

    Google Scholar 

  17. J. E. T. Corrie, A. Barth, V. R. N. Munasinghe, D. R. Trentham and M. C. Hutter, Photolytic cleavage 1-(2-nitrophenyl)ethyl ethers involves two parallel pathways and product release is rate-limited by decomposition of a common hemiacetal intermediate, J. Am. Chem. Soc., 2003, 125, 8546–8554.

    Article  CAS  Google Scholar 

  18. M. Schwörer and J. Wirz, Photochemical reaction mechanisms of 2-nitrobenzyl compounds in solution I. 2-Nitrotoluene: thermodynamic and kinetic parameters of the aci-nitro tautomer, Helv. Chim. Acta, 2001, 84, 1441–1457.

    Article  Google Scholar 

  19. A. P. Pelliccioli and J. Wirz, Photoremovable protecting groups: reaction mechanisms and applications, Photochem. Photobiol. Sci., 2002, 1, 441–458 and refs. cited therein.

    Article  Google Scholar 

  20. Y. V. Il’ichev, M. A. Schwörer and J. Wirz, Photochemical reaction mechanisms of 2-nitrobenzyl compounds: methyl ethers and caged ATP, J. Am. Chem. Soc., 2004, 126, 4581–4595.

    Article  Google Scholar 

  21. M. Gaplovsky, Y. V. Il’ichev, Y. Kamdzhilov, S. V. Kombarova, M. Mac, M. A. Schwörer and J. Wirz, Photochemical reaction mechanisms of 2-nitrobenzyl compounds: 2-nitrobenzyl alcohols form 2-nitroso hydrates by dual proton transfer, Photochem. Photobiol. Sci., 2005, 4, 33–42.

    Article  CAS  Google Scholar 

  22. S. Bühler, I. Lapoja, H. Giegrich, K.-P. Stengele and W. Pfleiderer, New types of very efficient photolyable protecting groups based upon the [2-(2-nitrophenyl)carbonyl (NPPOC) moiety, Helv. Chim. Acta, 2004, 87, 620–659.

    Article  Google Scholar 

  23. K. Schaper, S. Globisch and F. Bley, Systematic investigations of the photochemistry of o-nitrobenzyl compounds, Eur. J. Org. Chem., in press.

  24. T. J. DiMagno, M. H. B. Stowell and S. I. Chan, Nitrobenzene “caged” compounds as irreversible photoreductants: a rational approach to studying photoinduced intermolecular electron-transfer reactions in proteins, J. Phys. Chem., 1995, 99, 13038–13047.

    Article  CAS  Google Scholar 

  25. A. S. Dvornikov, C. M. Taylor, Y. C. Liang and P. M. Rentzepis, Photorearrangement mechanism of 1-nitro-naphthaldehyde and application of three-dimensional storage devices, J. Photochem. Photobiol., A, 1998, 112, 39–46.

    Article  CAS  Google Scholar 

  26. C. Grewer, J. Jäger, B. K. Carpenter and G. P. Hess, A new photoliable precursor of glycine with improved properties: a tool for chemical kinetic investigations of the glycine receptor, Biochemistry, 2000, 39, 2063–2070.

    Article  CAS  Google Scholar 

  27. R. Wieboldt, D. Ramesh, E. Jabri, A. Karplus, B. K. Carpenter and G. P. Hess, Synthesis and characterization of photolabile o-nitrobenzyl derivatives of urea, J. Org. Chem., 2002, 67, 8827–8831.

    Article  CAS  Google Scholar 

  28. A. Specht and M. Goeldner, 1-(o-nitrophenyl)-2,2,2-trifluoroethyl ether derivatives as stable and efficient photoremovable alcohol-protecting groups, Angew. Chem., Int. Ed., 2004, 43, 2008–2012.

    Article  CAS  Google Scholar 

  29. K. Schaper, D. Dommaschke, S. Globisch and S. A. Madani-Mobarekeh, AM1 calculations on the mechanism of the o-nitrobenzyl photochemistry, J. Inf. Rec., 2000, 25, 339–354.

    CAS  Google Scholar 

  30. F. Bley, K. Schaper and H. Görner, work in progress.

  31. G. J. Fisher and H. E. Johns, Pyridine photohydrates, in Photochemistry and Photobiology of Nucleic Acids, ed. S. Y. Wang, Academic Press, New York, 1976, pp. 169–224.

    Chapter  Google Scholar 

  32. H. Görner and D. Döpp, Photoinduced demethylation of 4-nitro- N, N-dimethylaniline, Photochem. Photobiol. Sci., 2002, 1, 270–277

    Article  Google Scholar 

  33. H. Görner, Photoreduction of nitronaphthalenes in benzene by N, N-dialkylanilines and triethylamine: a time-resolved UV-vis spectroscopic study, J. Chem. Soc., Perkin Trans. 2, 2002, 1778–1783.

    Article  Google Scholar 

  34. F. Wilkinson, W. P. Helman and A. B. Ross, Quantum yields for the photosensitized formation of the lowest electronically excited singlet state of molecular oxygen in solution, J. Phys. Chem. Ref. Data, 1993, 22, 113–275.

    Article  CAS  Google Scholar 

  35. B. G. Gowenlock, M. J. Maidment, K. G. Orrell, I. Prokes and J. A. Roberts, Nitroanisols. Sensitive indicators of dimerization criteria for C-nitrosoarenes, J. Chem. Soc., Perkin Trans. 2, 2001, 1904–1911.

    Google Scholar 

  36. H. Vancik, V. Bimunic-Meznaric, E. Mestrovic and I. Halasz, Nitrobenzene dimerizations as a model system for studying solid-state reaction mechanims, J. Org. Chem., 2004, 69, 4829–4834.

    Article  CAS  Google Scholar 

  37. J. E. T. Corrie, B. C. Gilbert, V. R. N. Munasinghe and A. C. Whitwood, EPR studies of the structure of transient radicals formed in photolytic reactions of some 2-nitrobenzyl compounds. Characterisation of aryl alkoxy aminoxyls and nitroaromatic radical-anions in the photolysis of caged ATP and related compounds, J. Chem. Soc., Perkin Trans. 2, 2000, 2483–2491.

    Article  Google Scholar 

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  1. Max-Planck-Institut für Bioanorganische Chemie, D-45413, Mülheim an der Ruhr, Germany

    Helmut Görner

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Görner, H. Effects of 4,5-dimethoxy groups on the time-resolved photoconversion of 2-nitrobenzyl alcohols and 2-nitrobenzaldehyde into nitroso derivatives. Photochem Photobiol Sci 4, 822–828 (2005). https://doi.org/10.1039/b506393k

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