ABSTRACT Thermal decomposition of transannular peroxide of anthracene (POA) (or 9,10-epidioxido anthracene) was studied by means of electron paramagnetic resonance spectroscopy (EPR) in the solid as well as in the liquid phases. Decomposition process proceeds via cleavage of the O-O bridge of the POA molecule, generating thus an alcoxy intermediate radical. Its concentration increases to a certain equilibrium stage during the time scale of the experiment. EPR spectra in the solid state were of the singlet type at the temperatures over 350 K, a doublet like anisotropic spectra were measured at the room temperature, both having g-value 2.0033. EPR spectrum from POA decomposed in benzene indicates four protons with higher (2aH = 0.305 mT, 2aH = 0.335 mT) and four protons with a lower (2aH = 0.075 mT, 2aH = 0.105 mT) splitting constants, corresponding well the radical expected after cleavage of O-O bridge.
Cite this paper
nullL. Lapčík, B. Lapčíková and A. Staško, "EPR Study of the Thermal Decomposition of Transannular Peroxide of Anthracene," International Journal of Organic Chemistry, Vol. 1 No. 2, 2011, pp. 37-40. doi: 10.4236/ijoc.2011.12007.
 J.S.K. Wan, R.N. McCormic, E.J. Baum, J.N. Pitts,Jr., “The Roles of Molecular Structure and Environment in the Reactivity of Excited States,“ Journal of the American Chemical Society, Vol. 87, No. 20, 1965, pp. 4409-4414.
 C.S. Foote, S. Wexler, “Singlet oxygen. A probable inter mediate in photosensitized autoxidations,“ Journal of the American Chemical Society, Vol. 86, No. 18, 1964, pp. 3880-3881.
 M. ?eppan, L. Lap?ík, M. Li?ka, P. Pelikán, ”Molecular orbital study of anthracene photooxidation,” European Polymer Journal, Vol. 16, No. 7, 1980, pp. 607-609.
 L. Lap?ík,Jr., L. Lap?ík, D. Bako?, V. Kell?, “Transannular peroxides of anthracene and its derivatives. Preparation, properties, and uses,” Chemicke Listy, Vol. 84, No. 6, 1990, pp. 582-605.
 R. Schmidt, K. Schaffner, W. Trost, H.D. Brauer, ”Wavelength-dependent and dual photochemistry of the endoperoxides of anthracene and 9,10-dimethylanthracene,” Journal of Physical Chemistry, Vol. 88, No. 5, 1984, pp. 956-958.
 H. Fidder, A. Lauer, W. Freyer, B. Koeppe, K. Heyne, “Photochemistry of Anthracene-9,10-endoperoxide,” Journal of Physical Chemistry A, Vol. 113, No. 22, 2009, pp. 6289-6296.
 S. Marku?, M. Lazár, L. Lap?ík, G. ?ík, L. Kompauer, CS Patent, No. 172837, 1978, pp. 1-10.
 L. Lap?ík, Jr., J. Schurz, “Photochemical degradation of hyaluronic acid by singlet oxygen,” Colloid and Polymer Science, Vol. 269, No. 6, 1991, pp. 633-635.
 Y. Nagaoka, K. Otsu, F. Okada, K. Sato, Y. Ohba, N. Kotani, J. Fujii, “Specific inactivation of cysteine protease-type cathepsin by singlet oxygen generated from naphthalene endoperoxides,” Biochemical and Biophysical Research Communications, Vol. 331, No. 1, 2005, pp. 215-223.
 A. Sta?ko, A. Bla?ková, V. Brezová, M. Breza, L. Lap?ík, L. Lap?ík, Jr., “Oxygen photosensitization in the presence of sodium anthracene-1-sulfonate,” Journal of Photochemistry and Photobiology A-Chemistry, Vol. 76, No. 3, 1993, pp. 159-165.
 C.S. Foote, S. Wexler, W. Ando, R. Higgins, “Chemistry of singlet oxygen. IV. Oxygenations with hypochlorite-hydrogen peroxide,” Journal of the American Chemical Society, Vol. 90, No. 4, 1968, pp. 975-981.
 I. Gillet, “Ultraviolet absorption spectra of the photo-oxides of anthracene and naphthalene,” Bulletin de la Societe Chimique de France, Vol. 17, 1950, pp. 1135-1141.
 K. Lonsdale, E. Nave, J.F. Stephens, “X-ray studies of a single crystal chemical reaction photo oxide of anthracene to (anthraquinone, anthrone),” Philosophical Transactions of the Royal Society of London Series A-Mathematical and Physical Sciences, Vol. 261, No. 1114, 1966, pp. 1-31.
 G.W. Cowell, J.N. Pitts, Jr., “Photochemical studies in rigid matrixes. II. A study of the photochemical reactivity of anthracene in polystyrene and the development of an o-nitrobenzaldehyde actinometer in poly(methyl methacrylate),” Journal of the American Chemical Society, Vol. 90, No. 5, 1968, pp. 1106-1110.
 “CRC Handbook of Spectra from Quinones and Quinols”, CRC Press, Boca Raton, 1971.