Aromatic hydroxylation by Fenton reagents (reactive intermediate [Lx+FeIIOOH(BH+)], not free hydroxyl radical (HO.)).
Several iron complexes [FeII(bpy)2(2+), FeII(OPPh3)4(2+), and FeII(PA)2] in combination with hydrogen peroxide (HOOH) catalytically hydroxylate aromatic substrates (ArH). The base-induced nucleophilic addition of HOOH to the electrophilic iron center yields the reactive intermediate of Fenton reagents [FeIILx2+ + HOOH<-->Lx+FeIIOOH(BH+)(1)]. The latter includes a 'stabilized' hydroxyl radical that is able to replace an aromatic hydrogen (H) with a hydroxyl group (HO) via an initial addition reaction. With PhCH3 and PhCH2CH3 as substrates free HO. (from the radiolysis of H2O) reacts via aryl addition (97 and 85%, respectively) to give Ar-Ar as the predominant product, whereas 1 favors H-atom abstraction from the alkyl group (50 and 80%, respectively) and the only detectable products from aryl addition are the respective substituted phenols (o:p-ArOH). Other substituted benzenes (PhX) undergo addition by free HO at the ortho and para aryl carbons (o:p ratio, 2), followed by dimerization and elimination of two H2O molecules to yield substituted biphenyls. In contrast, 1 reacts with PhX to yield substituted phenol (ArOH; o:p ratio, 0.5-1.1). With phenol (PhOH) as the substrate, reaction with 1 yields mainly catechol (o-Ar(OH)2; o:p ratio, 20). In a solvent matrix of MeCN:H2O (3:1 mol:mol ratio) the reaction efficiencies with FeII(bpy)2(2+) and FeII(OPPh3)4(2+) for the hydroxylation of benzene to phenol are 36 and 42%, respectively (product per HOOH).
Hage
J P
JP
Department of Chemistry, Texas A&M University, College Station 77843-3255, USA.
Llobet
A
A
Sawyer
D T
DT
D001554:Benzene / Q000737:chemistry; D006838:Hydrocarbons / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry*; D017665:Hydroxyl Radical; D006900:Hydroxylation; D007202:Indicators and Reagents; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D012997:Solvents
C045076:Fenton's reagent; D006838:Hydrocarbons; D007202:Indicators and Reagents; D012997:Solvents; D017665:Hydroxyl Radical; D006861:Hydrogen Peroxide; D007501:Iron; D001554:Benzene