1975-14-0Relevant articles and documents
REACTION OF 2,4,6-TRI-TERT-BUTYLPHENOXYL WITH OXYGEN IN THE PRESENCE OF METAL COMPOUNDS
Vol'eva, V. B.,Ivanov, E. V.,Batanov, I. A.,Ershov, V. V.
, p. 648 - 650 (1986)
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Stewart,Poh
, p. 3437,3441 (1972)
Combining Structural with Functional Model Properties in Iron Synthetic Analogue Complexes for the Active Site in Rabbit Lipoxygenase
Dobbelaar, Emiel,Rauber, Christian,Bonck, Thorsten,Kelm, Harald,Schmitz, Markus,De Waal Malefijt, Matina Elo?se,Klein, Johannes E. M. N.,Krüger, Hans-J?rg
supporting information, p. 13145 - 13155 (2021/09/03)
Iron complexes that model the structural and functional properties of the active iron site in rabbit lipoxygenase are described. The ligand sphere of the mononuclear pseudo-octahedral cis-(carboxylato)(hydroxo)iron(III) complex, which is completed by a tetraazamacrocyclic ligand, reproduces the first coordination shell of the active site in the enzyme. In addition, two corresponding iron(II) complexes are presented that differ in the coordination of a water molecule. In their structural and electronic properties, both the (hydroxo)iron(III) and the (aqua)iron(II) complex reflect well the only two essential states found in the enzymatic mechanism of peroxidation of polyunsaturated fatty acids. Furthermore, the ferric complex is shown to undergo hydrogen atom abstraction reactions with O-H and C-H bonds of suitable substrates, and the bond dissociation free energy of the coordinated water ligand of the ferrous complex is determined to be 72.4 kcal·mol-1. Theoretical investigations of the reactivity support a concerted proton-coupled electron transfer mechanism in close analogy to the initial step in the enzymatic mechanism. The propensity of the (hydroxo)iron(III) complex to undergo H atom abstraction reactions is the basis for its catalytic function in the aerobic peroxidation of 2,4,6-tri(tert-butyl)phenol and its role as a radical initiator in the reaction of dihydroanthracene with oxygen.
Electron transfer between protonated and unprotonated phenoxyl radicals
Omura, Kanji
, p. 858 - 867 (2008/09/19)
(Chemical Equation Presented) The reaction of phenoxyl radicals with acids is investigated. 2,4,6-Tri-tert-butylphenoxyl radical (13), a persistent radical, deteriorates in MeOH/PhH in the presence of an acid yielding 4-methoxycyclohexa-2,5-dienone 18a and the parent phenol (14). The reaction is facilitated by a strong acid. Treatment of 2,6-di-tert-butyl-4-methylphenoxyl radical (2), a short-lived radical, generated by dissociation of its dimer, with an acid in MeOH provides 4-methoxycyclohexa-2,5-dienone 4 and the products from disproportionation of 2 including the parent phenol (3). A strong acid in a high concentration favors the formation of 4 while the yield of 3 is always kept high. Oxidation of the parent phenol (33) with PbO2 to generate transient 2,6-di-tert-butylphenoxyl radical (35) in AcOH/H2O containing an added acid provides eventually p-benzoquinone 39 and 4,4′-diphenoquinone 42, the product from dimerization of 35. A strong acid in a high concentration favors the formation of 39. These results suggest that a phenoxyl radical is protonated by an acid and electron transfer takes place from another phenoxyl radical to the protonated phenoxyl radical, thus generating the phenoxyl cation, which can add an oxygen nucleophile, and the phenol (eq 5). The electron transfer is a fast reaction.
A New Methodology for the Bis(oxocyclohexadienyl) Peroxide Formation
Omura, Kanji
, p. 8790 - 8793 (2007/10/03)
Symmetrically substituted bis(4-oxocyclohexa-2,5-dienyl) peroxide 5 (R = R') as well as unsymmetrically substituted 5 (R ≠ R') can be prepared efficiently by treating 4-halogenocyclohexa-2,5-dienone 3 with 4-hydroperoxycyclohexa-2,5-dienone 4 in the presence of an appropriate positive halogen compound such as N-iodosuccinimide. Acetonitrile is a suitable solvent for the reaction. The formation of 5 is suggested to take place via electrophilic attack by the positive halogen species upon 3 generating the 4-oxocyclohexa-2,5-dienyl cation (or the phenoxy cation), followed by nucleophilic attack by 4 upon the cation. It is emphasized that some of the peroxides obtained by this means have not been prepared by the classical method, coupling of phenoxy radicals with O2.