Add time:07/27/2019         Source:sciencedirect.com

The 5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)-porphine-Mn(III) chloride (F20TPPMn(III)Cl) catalyzed oxidation of 2,4,6-tri-tert-butylphenol (TTBP) by pentafluoroiodosylbenzene (C6F5IO) in dichloromethane (CH2Cl2) and acetonitrile (CH3CN) medium was studied. The reactive intermediates of these reactions were trapped by 2,4,6-tri-tert-butylphenol (TTBP) with formation of 2,4,6-tri-tert-butylphenoxy radical (TTBP. radical). It was noted that the formation of TTBP. radical in CH2Cl2 was distinctly biphasic in nature, demonstrating the presence of two intermediates. Whereas the same reaction became monophasic in more polar acetonitrile medium. The rate constants for the formation of TTBP. radical in CH2Cl2 were dependent on the substrate (TTBP) concentrations. However, the rate constants of the formation of TTBP. radical (15±1×10-3 s-1) in CH3CN solvent is independent of TTBP concentrations. The rate constants for CH3CN solvents were calculated directly from –ln(A∞-At) vs. time (t) plots. For CH2Cl2 solvent the biphasic plot was analyzed in two steps.

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