meso-TETRAPHENYLIRONPORPHYRIN(III) CHLORIDE CATALYZED OXIDATION OF ANILINE AND ITS SUBSTITUENTS BY m-CHLOROPERBENZOIC ACID
نویسندگان
چکیده
The most fascinating feature of heme-enzymes such as cytochromes P450 is their ability to carry out oxidations with high selectivity. Metalloporphyrin complexes are used as replicate compounds for cytochrome P450. A kinetic analysis has been carried out with the aim of understanding the mechanistic studies on oxidation of anilines by m-chloroperbenzoic acid catalyzed by meso-tetraphenylironporphyrin(III) chloride in aqueous acetic acid medium. The order of the reaction is found to be second order with respect to the substrate and first order with respect to the catalyst and oxidant. Product analysis proves that azobenzene is the sole product in the catalytic oxidation. The increase of [H+] in this oxidation retards the rate of the reaction. The effects of substituents on the oxidation rate are studied with 19 ortho-, metaand parasubstituted anilines at five different temperatures. The thermodynamic parameters for the oxidation have been determined and discussed. The catalysed m-chloroperbenzoic acid oxidation with substituted anilines fulfills the isokinetic relationship and Exner correlation but not to any of the linear free energy relationships. The solvent interaction also plays a major role in leading the reactivity. Based on the kinetic results and product analysis a probable mechanism is proposed.
منابع مشابه
Catalytic Synthesis of Hydroquinone by Using Rh on Al2O3 Via Different Rout
The catalytic synthesis of hydroquinoneutilize benzene as the starting material. The manufacture of hydroquinone by oxidation of phenol and 1,2diisopropylbenzene. The first route begin with Friedel-Crafts alkylation of petroleum –derived benzene to afford cumene. Subsequent Hock-type, air oxidation of the cumene leads to formation of acetone and phenol. The phenol is oxidized by using 70%hydrog...
متن کاملElectrocatalytic oxidation of formaldehyde on novel composite of nickel/triton-x100/poly(o-aminophenol-co-aniline)
Oxidation of formaldehyde (HCHO) is very important, owing to its use in fuel cells. Modification of electrodes surfaces is an excellent way to decrease the overpotentials as well as to increase the current density of the voltammetric response.pt as most efficient metal catalyst can easily be poisoned by product of oxidation and also it has high cost. In this work an efficient and low cost elect...
متن کاملDual Behavior of Iodine Species in Condensation of Anilines and Vinyl Ethers Affording 2-Methylquinolines.
A metal-free, mild and efficient method for the synthesis of 2-methylquinolines was successfully developed by condensation of anilines with vinyl ethers in the presence of catalytic amount of iodine. Modification of both pyridine and benzene moieties was easily achieved by changing only the vinyl ether and aniline. In this reaction, the iodine species was revealed to show dual behavior; molecul...
متن کاملPhotophysical properties of a new series of water soluble iridium bisterpyridine complexes functionalised at the 4' position.
Four new hetero- and homo-leptic iridium(III) bisterpyridine complexes have been prepared which incorporate aniline (tpy-φ-NH(2)), benzoic acid (tpy-φ-COOH), and benzyl alcohol (tpy-φ-CH(2)OH) substituents at the 4' positions of the tpy ligands (tpy = 2,2':6',2''-terpyridine, φ = phenylene). The electrochemical behaviour and ground and excited state spectroscopic properties of the complexes are...
متن کاملAn efficient green synthesis of highly substituted imidazoles catalyzed by Al-MCM-41 nanoreactors
Al-MCM-41 nanoreactors is found to be a remarkable efficient catalyst for one-pot multicomponent cyclocondensation of benzil, aniline or ammonium acetate and aromatic aldehydes for the synthesis of polysubstituted imidazoles under solvent-free conditions. The reaction was efficiently promoted by 10 mg nano-Al-MCM-41 and the heterogeneous catalyst was recycled for four runs in this reaction with...
متن کامل