15552-69-9Relevant academic research and scientific papers
Iron(II, III)-catalyzed oxidative N-dealkylation of amines with dioxygen
Narog, Dorota,Lechowicz, Urszula,Pietryga, Tadeusz,Sobkowiak, Andrzej
, p. 25 - 33 (2004)
A study on the oxidation of N,N-dimethylaniline and other alkylated anilines by dioxygen, air, and hydrogen peroxide catalyzed by several labile Fe complexes in acetonitrile was carried out. N,N-dimethylaniline (DMA) was oxidized to N-methylaniline and formaldehyde as well as to N-methylanilide. Formaldehyde and the excess of substrate underwent condensation reaction to produce 4,4′-methylenebis(N,N-dimethylaniline). Small quantities of N-methylformanilide and formanilide were also formed during oxidation of N,N-dimethylaniline and N-methylaniline, respectively. The system was very labile even in the presence of bpy as a ligand and it was difficult to formulate the nature of the reactive species. However, the results confirmed that Fe(III) was reduced by the substrate to Fe(II), which interacted with substrate and activated dioxygen for demethylation process.
Iron(II)-induced activation of 1:1 HOOH/HCl for the chlorohydroxylation of olefins and the chlorination of hydrocarbons: Chlorinated fenton chemistry
Sawyer, Donald T.,Hage, John P.,Sobkowiak, Andrzej
, p. 106 - 109 (2007/10/02)
Iron complexes [FeII(OPPh3)42+, FeII(bpy)2,2+, FeII(OH2)62+, and FeIIICl3] catalytically activate 1:1 HOOH/ HCl combinations for the efficient chlorohydroxylation of olefins. The reactive intermediate 7 is not HOCl, but appears to be formed via a Fenton process FeIILx2+ ? (B) [Lx+FeIIOOH(BH+)] (1) → (HCl) [LxFeIV(OH)Cl] (7) + H2O}. Although the major product from the reaction of 7 with olefin substrates (e.g., cyclohexene, C-C6H10) is the chlorohydroxo derivative [C-C6H10 + HOOH + HCl → (FeIILx) c-C6H10(OH)Cl + H2O], significant amounts of the dihydroxo [c-C6H10(OH)2] and traces of the dichloro [c-C6H10Cl2] derivatives are produced. The reaction efficiency with respect to HOOH/HC1 ranges from 51% for norbornene to 31% for cyclohexene to 10% for 1-hexene. The presence of dioxygen (O2) with c-C6H10 results in the production of some ketone [c-C6H8(O)] via oxygenated Fenton chemistry, but does not inhibit the chlorohydroxylation process. The catalyzed process is equally efficient and selective in a biphasic H2O/substrate solution as in acetonitrile. With cis-stilbene (cis-PhCH=CHPh) the major product is the epoxide (>80%); the reaction efficiency is 63% relative to HOOH/HCl. These systems chlorinate saturated hydrocarbons (c-C6H12 → c-C6H11Cl) and hydroxylate benzene (PhH → PhOH). Because 7 chlorohydroxylates olefins and chlorinates hydrocarbons in aqueous media much more efficiently than HOCl, its in-vivo analogue may be a reasonably reactive intermediate for "oxy-radical" damage in biological systems.
Pressure-Dependent Aquation of the Tris(2,2'-bipyridyl)iron(II) Cation
Lawrance, Geoffrey A.,Stranks, Donald R.,Sullivan, Terence R.
, p. 1763 - 1768 (2007/10/02)
The aquation of Fe(bpy)32+ (bpy = 2,2'-bipyridyl) was studied in aqueous hydrochloric acid at a range of pressure between 1 and 2070 bar.Activation volumes (ΔV) in 1.0 MHCl (+12.3 cm3mol-1), 0.01 M HCl (+14.8 cm3mol-1), 1.0 M DCl (+13.3 cm3mol-1) and 0.01 M HCl (+16.3 cm3mol1-) were determined.A mechanism involving a significant positive contribution to ΔV arising from a low-spin high-spin preequilibrium is proposed.The minor effect of the deuterium solvent isotope on ΔV is consistent with this proposal.
