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Abstract:

Photosensitized reaction of xanthinic compounds (XH) as caffeine (CF), theobromine (TB) and theophylline (TF) by benzophenone (BZ) in ethanol solution was investigated. In the three cases four main reaction products (benzopinacol; diphenylcarbinol; 1,1-diphenyl-1,2-propanediol and 8-[1-(1-hydroxyethyl)] xanthine) were identified and then characterized by melting point, 1H NMR, 13C NMR and mass spectrometry. The quenching of triplet BZ by the three XH was detected and a thorough kinetic analysis was performed. Caffeine produces mainly physical quenching, while TF reacts by N-H hydrogen abstraction. For TB both mechanisms are operative. Heats of reactions were calculated for chosen reactive steps of the mechanism by the PM3 method. They provide additional support to the proposed reaction scheme. We demonstrate that the mechanism leading to XP formation does not proceed through the X• radical directly obtained by H abstraction. An alternative reaction path through an intermediate radical originated on the addition of ethanol radical to XH is proposed. Redox potentials for the oxidation of XH were estimated by cyclic voltametry and by using the Rehm-Weller equation the redox quenching of triplet BZ by XH was discarded.

Registro:

Documento: Artículo
Título:Benzophenone-Photosensitized Reactions of Xanthinic Compounds. A Mechanistic Study
Autor:Murgida, D.H.; Aramendía, P.F.; Erra-Balsells, R.
Filiación:Depto. de Quim. Orgánica, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428, Buenos Aires, Argentina
Depto. de Quim. Orgánica, Universidad de Buenos Aires, Buenos Aires, Argentina
INQUIMAE, Depto. Quim. Inorg., Analitica y Q., Universidad de Buenos Aires, Buenos Aires, Argentina
Año:1998
Volumen:67
Número:5
Página de inicio:487
Página de fin:494
DOI: http://dx.doi.org/10.1111/j.1751-1097.1998.tb09444.x
Título revista:Photochemistry and Photobiology
Título revista abreviado:Photochem. Photobiol.
ISSN:00318655
CODEN:PHCBA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00318655_v67_n5_p487_Murgida

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Citas:

---------- APA ----------
Murgida, D.H., Aramendía, P.F. & Erra-Balsells, R. (1998) . Benzophenone-Photosensitized Reactions of Xanthinic Compounds. A Mechanistic Study. Photochemistry and Photobiology, 67(5), 487-494.
http://dx.doi.org/10.1111/j.1751-1097.1998.tb09444.x
---------- CHICAGO ----------
Murgida, D.H., Aramendía, P.F., Erra-Balsells, R. "Benzophenone-Photosensitized Reactions of Xanthinic Compounds. A Mechanistic Study" . Photochemistry and Photobiology 67, no. 5 (1998) : 487-494.
http://dx.doi.org/10.1111/j.1751-1097.1998.tb09444.x
---------- MLA ----------
Murgida, D.H., Aramendía, P.F., Erra-Balsells, R. "Benzophenone-Photosensitized Reactions of Xanthinic Compounds. A Mechanistic Study" . Photochemistry and Photobiology, vol. 67, no. 5, 1998, pp. 487-494.
http://dx.doi.org/10.1111/j.1751-1097.1998.tb09444.x
---------- VANCOUVER ----------
Murgida, D.H., Aramendía, P.F., Erra-Balsells, R. Benzophenone-Photosensitized Reactions of Xanthinic Compounds. A Mechanistic Study. Photochem. Photobiol. 1998;67(5):487-494.
http://dx.doi.org/10.1111/j.1751-1097.1998.tb09444.x