OH Radical as a Probe of the Spin Polarizability in 1- and 2-Naphthol.

The relative yields for addition of the OH radical at the various positions of 1- and 2-naphthol provide a measure of the spin polarizability in the naphthols. The observed yields show that addition occurs predominantly at the naphthol positions that are conjugated with the OH substituent. They also show that the electronic structures of the naphthols are significantly affected by a concerted interaction between the OH substituent and the unsubstituted ring and that this effect is somewhat greater when the OH substituent is adjacent to the naphthol bridge. The yields for addition at the different naphthol positions correlate with the local spin polarizabilities at reactive carbons in the naphthol. The spin polarizability may be a general property governing the reactivity of closed-shell molecules with radicals.

Absorption spectrum, mass spectrometric properties, and electronic structure of 1,2-benzoquinone.

Absorption spectrophotometric and mass spectrometric properties of 1,2-benzoquinone, prepared in aqueous solution by the hexachloroiridate(IV) oxidation of catechol and isolated by HPLC, are reported. Its absorption spectrum has a broad moderately intense band in the near UV with an extinction coefficient of 1370 M(-1)cm(-1) at its 389 nm maximum. The oscillator strength of this band contrasts with those of the order-of-magnitude stronger approximately 250 nm bands of most 1,4-benzoquinones. Gaussian analysis of its absorption spectrum indicates that it also has modestly intense higher energy bands in the 250-320 nm region. In atmospheric pressure mass spectrometric studies 1,2-benzoquinone exhibits very strong positive and negative mass 109 signals that result from the addition of protons and hydride ions in APCI and ESI ion sources. It is suggested that the hydride adduct is formed as the result of the highly polar character of ortho-quinone. On energetic collision the hydride adduct loses an H atom to produce the 1,2-benzosemiquinone radical anion. The present studies also show that atmospheric pressure mass spectral patterns observed for catechol are dominated by signals of 1,2-benzoquinone resulting from oxidation of catechol in the ion sources. Computational studies of the electronic structures of 1,2-benzoquinone, its proton and hydride ion adducts, and 1,2-benzosemiquinone radical anion are reported. These computational studies show that the structures of the proton and hydride adducts are similar and indicate that the hydride adduct is the proton adduct of a doubly negatively charged 1,2-benzoquinone. The contrast between the properties of 1,2- and 1,4-benzoquinone provides the basis for considerations on the effects of conjugation in aromatic systems.

Determination of the spectroscopic properties and chromatographic sensitivities of substituted quinones by hexachlorate(IV) oxidation of hydroquinones.

HPLC studies of the oxidation of substituted hydroquinones show that the corresponding quinones can, in most cases, be produced quantitatively by two electron transfer to hexachloroiridate(IV). As a consequence the chromatographic and spectroscopic properties of substituted quinones that are not readily available can be determined without the necessity of preparation of an isolatable sample. Absorption spectra and extinction coefficients of bromoquinone, chloroquinone, hydroxyquinone and carboxyquinone anion at pH 7 are reported as illustrative examples. All have intense absorption bands at approximately 250nm that are characteristic of quinones. Oxidation of carboxyhydroquinone at low pH is, however, anomalous in that a hydroxylated carboxyquinone is produced as the result of four electron transfer to hexachloroiridate.

Hydroxyl radical as a probe of the charge distribution in aromatics: phenol.

Initial radiation chemical yields of 1.48 (2), 0.24 (2), and 2.01 molecules per 100 eV of absorbed energy are reported for addition of *OH radical to each of the ortho, meta, and para positions of phenol. These yields represent 91% of the yield of 5.96 expected for *OH addition to 5 mM phenol and are in general agreement with other previous measurements. Pulse radiolysis experiments show that phenoxy radical is produced in a yield of approximately 0.42 as a result of addition of *OH at phenol's ipso position. The total of these yields (5.84) accounts for the addition of virtually all of the expected *OH radicals. The relative yields for addition to the ortho, meta, and para positions provide a measure of the charge distribution in phenol that correlates quite well with the unpaired spin distribution in phenoxyl radical. This correlation indicates that the OH substituent similarly affects the charge distribution on the aromatic ring of phenol and the unpaired spin distribution in the phenoxyl radical.

Concerted effects of substituents in the reaction of .OH radicals with aromatics: the cresols.

The concerted effects of hydroxyl and methyl substituents in controlling the site of .OH radical attack on aromatics in aqueous solutions are explored using the cresols as typical examples. The distributions of dihydroxytoluenes produced in the radiolysis of aqueous solutions of the cresols containing ferricyanide as a radical oxidant were examined by capillary electrophoretic and liquid chromatographic methods. Because .OH is a strong electrophile, it adds preferentially at the electron-rich sites of an aromatic ring. As a result, the observed distributions of dihydroxytoluenes reflect the charge distributions in the cresols. It is shown that in the case of m-cresol the hydroxyl substituent has a dominant ortho-para directing effect similar to that observed for phenol. In o- and p-cresol, this effect is modified, indicating that the methyl substituent has a significant effect on the electronic structure of those cresols. Correlation of the charge distribution in the cresols indicated by the observed distribution of dihydroxytoluenes with the unpaired spin distribution in the corresponding methylphenoxyl radicals demonstrates that the electronic structures of o- and p-cresol and their corresponding phenoxyl radicals are similarly affected by hydroxyl and methyl substitution. Addition of .OH at the methyl-substituted positions of o- and p-cresol to produce o- and p-dienone is also reported. The observation of these dienones demonstrates that addition of .OH at the ipso positions of alkylated aromatics can be of considerable importance. Mass spectrometric studies show that these dienones have relatively higher proton affinities than their isomeric analogues.