Chemical, pulse radiolysis and density functional studies of a new, labile 5,6-indolequinone and its semiquinone.
The chemical and spectroscopic characterization of 5,6-indolequinones and their semiquinones, key transient intermediates in the oxidative conversion of 5,6-dihydroxyindoles to eumelanin biopolymers, is a most challenging task. In the present paper, we report the characterization of a novel, relatively long-lived 5,6-indolequinone along with its semiquinone using an integrated chemical, pulse radiolytic, and computational approach. The quinone was obtained by oxidation of 5,6-dihydroxy-3-iodoindole (1a) with o-chloranil in cold ethyl acetate or aqueous buffer: it displayed electronic absorption bands around 400 and 600 nm, was reduced to 1a with Na2S2O4, and reacted with o-phenylenediamine to give small amounts of 3-iodo-1H-pyrrolo[2,3-b]phenazine (2). The semiquinone exhibited absorption maxima at 380 nm (sh) and 520 nm and was detected as the initial species produced by pulse radiolytic oxidation of 1a at pH 7.0. DFT investigations indicated the 6-phenoxyl radical and the N-protonated radical anion as the most stable tautomers for the neutral and anion forms of the semiquinone, respectively. Calculated absorption spectra in water gave bands at 350 (sh) and 500 nm for the neutral form and at 310 and 360 (sh) nm for the anion. Disproportionation of the semiquinone with fast second-order kinetics (2k = 1.1 x 1010 M-1 s-1) gave a chromophore with absorption bands resembling those of chemically generated 1a quinone. Computational analysis predicted 1a quinone to exist in vacuo as the quinone-methide tautomer, displaying low energy transitions at 380 and 710 nm, and in water as the o-quinone, with calculated absorption bands around 400 and 820 nm. A strong participation of a p orbital on the iodine atom in the 360-380 nm electronic transitions of the o-quinone and quinone-methide was highlighted. The satisfactory agreement between computational and experimental electronic absorption data would suggest partitioning of 1a quinone between the o-quinone and quinone-methide tautomers depending on the medium.
Pezzella
Alessandro
A
Department of Organic Chemistry and Biochemistry, University of Naples Federico II, Via Cintia, I-80126 Naples, Italy. alessandro.pezzella@unina.it
Crescenzi
Orlando
O
Natangelo
Anna
A
Panzella
Lucia
L
Napolitano
Alessandra
A
Navaratnam
Suppiah
S
Edge
Ruth
R
Land
Edward J
EJ
Barone
Vincenzo
V
d'Ischia
Marco
M
D000085:Acetates / Q000737:chemistry; D000107:Acetylation; D016227:Benzoquinones / Q000138:chemical synthesis*; D002703:Chloranil / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D002855:Chromatography, Thin Layer; D004563:Electrochemistry; D007202:Indicators and Reagents; D045563:Indolequinones / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D011675:Pulse Radiolysis; D013056:Spectrophotometry, Ultraviolet
D000085:Acetates; D016227:Benzoquinones; D007202:Indicators and Reagents; D045563:Indolequinones; D002703:Chloranil; C007650:ethyl acetate