Abstract:A practical model was developed for liquid-phase Mn 3+catalysed oxidation of ethyl benzene by O 2 . The model describes time profiles of concentrations of ethyl benzene and two intermediate oxidation products (methyl phenyl carbinol and acetophenone). The kinetic model of acetophenone oxidation to benzoic acid was also obtained. The influence of the main products of the ethyl benzene oxidation on the reaction kinetics is discussed. It was established that the addition of ethyl benzene hydroperoxide does not af… Show more
“…The kinetic study of aerobic and anaerobic oxidation of acetophenone by manganese triacetate showed that both reactions obey the same rate law: r = k [R‘CO][Mn 3+ ], where k is the rate constant of the reaction of Mn 3+ with acetophenone. Moreover, the rates of acetophenone consumption under aerobic and anaerobic conditions are equal …”
Section: Oxidation Of Hydrocarbons In Nonpolar Mediamentioning
The work discussed the role of cobalt and manganese complexes
in the liquid-phase catalytic benzylic oxidation in polar and
apolar media. Evidence that hydrocarbon is involved during
oxidation with the transition metal ion is presented. It is
supposed that reaction acceleration caused by bromide salts is
due to the increase in the rate of the electron transfer and no
initiation by bromine atoms exist. The reasons for different
product selectivity in the presence of cobalt and manganese are
explained and the synergistic effects of mixed catalysts are
discussed. Thus cobalt is active in the oxidation of hydrocarbons
and alcohols, while manganese is active in oxidation of carbonyl
compounds. These assumptions allowed to build a system of
differential rate equations.
“…The kinetic study of aerobic and anaerobic oxidation of acetophenone by manganese triacetate showed that both reactions obey the same rate law: r = k [R‘CO][Mn 3+ ], where k is the rate constant of the reaction of Mn 3+ with acetophenone. Moreover, the rates of acetophenone consumption under aerobic and anaerobic conditions are equal …”
Section: Oxidation Of Hydrocarbons In Nonpolar Mediamentioning
The work discussed the role of cobalt and manganese complexes
in the liquid-phase catalytic benzylic oxidation in polar and
apolar media. Evidence that hydrocarbon is involved during
oxidation with the transition metal ion is presented. It is
supposed that reaction acceleration caused by bromide salts is
due to the increase in the rate of the electron transfer and no
initiation by bromine atoms exist. The reasons for different
product selectivity in the presence of cobalt and manganese are
explained and the synergistic effects of mixed catalysts are
discussed. Thus cobalt is active in the oxidation of hydrocarbons
and alcohols, while manganese is active in oxidation of carbonyl
compounds. These assumptions allowed to build a system of
differential rate equations.
“…Using hydrogen peroxide and a tungsten catalyst, cyclohexanol is oxidized to cyclohexanone, a Baeyer−Villiger oxidation occurs followed by hydrolysis, and the product hydroxyl acid is oxidized further to the diacid ( 306 ). The oxidation of ethylbenzene to benzoic acid using oxygen and a manganese catalyst was reported, and the kinetics of this process were studied carefully. − 71 Baeyer−Villiger Oxidations in Oxidation Cascades…”
Section: 75 Baeyer−villiger Reactionmentioning
confidence: 99%
“…The oxidation of ethylbenzene to benzoic acid using oxygen and a manganese catalyst was reported, and the kinetics of this process were studied carefully. [134][135][136] Baeyer-Villiger oxidation in concert with benzylic oxidation was utilized to produce 311 from 310 (Scheme 72). 137 In the synthesis of a related compound (313), Lyttle also employed a Baeyer-Villiger oxidation of aldehyde 312.…”
“…Therefore, the selectivity of AcPO was lower with p-TFBQ/NHPI than those with p-TCBQ/NHPI and p-TBBQ/NHPI, respectively. Meanwhile, the homolytic cleavage of O-O bond of PEHP could occur in the process of reaction [20]. PEA was formed through RO abstracting a H atom from NHPI, QH or alkane [10].…”
Section: Catalytic Activity Of Substituted Benzoquinone In Ethylbenzementioning
Quinones with electron-withdrawing F, Cl or Br groups and N-hydroxyphthalimide (NHPI) were used as catalysts in selective oxidation of hydrocarbons with molecular oxygen as oxidant. The catalytic activity in the selective oxidation of ethylbenzene to oxygenation products was in the following order: p-benzoquinone\tetrafluoro-pbenzoquinone & tetrachloro-p-benzoquinone\tetrabromo-p-benzoquinone (p-TBBQ). Moderate electron-withdrawing power of substituent was suitable for quinone abstracting hydrogen from NHPI to generate reactive phthalimido-Noxyl (PINO). The catalytic activity of p-TBBQ/NHPI, the best catalyst in our study, was also tested in the selective oxidation of alkylarenes, alkenes and alkanes.
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