The role of N-hydroxyphthalimide in the reaction mechanism of liquid-phase oxidation of p-cymene

Сапунов, В. Н.; Koshel, G. N.; Rumyantseva, Yu. B.; Курганова, Е. А.; Kukushkina, N. D.

doi:10.1134/s0965544113030092

Cited by 12 publications

(4 citation statements)

References 8 publications

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“…Most recently, Koshel' and his coworkers 131 have investigated the role of NHPI in the oxidation of p-cymene to its hydroperoxide, affording up to 95% selectivity at a conversion of 25-30%. To implement the NHPI catalysis for industrial usability, Punta and his coworkers 132 have reported the initiator-free oxidation of cumene to its hydroperoxide catalyzed by NHPI with physical adsorbent resins Amberlysts, affording >30% conversion and >90% selectivity.…”

Section: No Initiatorsmentioning

confidence: 99%

Metal-free allylic/benzylic oxidation strategies with molecular oxygen: recent advances and future prospects

et al. 2014

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The selective oxo-functionalization of hydrocarbons under mild conditions with molecular oxygen as the terminal oxidant continues to be a hot topic in organic synthesis and industrial chemistry. Though many oxidation protocols in combination with transition metal salts, enzymes, organometallic catalysts, or organocatalysts have been summarized recently, a review that focuses solely on the metal-free allylic/ benzylic oxidation strategies with molecular oxygen is still unavailable. This critical review will summarize recent significant advances achieved in this important field under the scope of green chemistry, which covers the promising applications and brief mechanistic profiles involving three kinds of efficient catalysts, namely N-hydroxyimides, homogeneous/heterogeneous light-sensitive molecules, and heteroatomdoped carbon materials, and concerns the sustainability of these methods, as well as predicts the potential utilization of available but unreported analogous catalysts or catalytic systems in this field. Special emphasis will also be placed on the burgeoning metal-free strategies with visible light irradiation from the long-term greenness and sustainability of these oxidation processes due to their established appealing performances under ambient conditions.

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Section: No Initiatorsmentioning

confidence: 99%

Metal-free allylic/benzylic oxidation strategies with molecular oxygen: recent advances and future prospects

et al. 2014

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“…So, Eqs. and reflecting how the hydrocarbon is involved in the process are accordingly adjusted with terms accounting for the new reaction pathway :

\begin{matrix} true \\ right - \frac{normald ([], RH)}{normald italict} & = & left ((), k_{0} ([], RH) + k_{01} ([], NHPI)) \cdot ([], {ROO}^{•}) \\ left + f \cdot k_{1} ([], ROOH) + r_{0} \end{matrix}

\begin{matrix} true \\ right \frac{d [ROOH]}{d t} & = & left ((), k_{0} ([], RH) + k_{01} ([], NHPI)) \cdot ([], {ROO}^{•}) \\ left - k_{1} ([], ROOH) \end{matrix}

\begin{matrix} true \\ right ([], {ROO}^{•}) = \frac{\sqrt{{italicr}_{0} + f \cdot {italick}_{1} [ROOH]}}{\sqrt{2 {italick}_{normalt}}} \end{matrix}

…”

Section: Experimental Methods and Analysismentioning

confidence: 99%

“…So, Eqs. (1) and (2) reflecting how the hydrocarbon is involved in the process are accordingly adjusted with terms accounting for the new reaction pathway [27]:…”

Section: Mathematical Modeling and Calculation Proceduresmentioning

confidence: 99%

“…Recently , similar questions have also been raised by authors who had earlier supported the idea that NHPI has initiator properties. However, analysis of data for the oxidation of cumene , indicate, clearly, that the presence of NHPI is definitely influential in increasing initiation rates. Thus, it is still, currently, a challenging task to fully answer the questions as to what the role of NHPI is in all stages of oxidation.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics and Mechanism of Cumene Oxidation Initiated by N‐Hydroxyphthalimide

Сапунов

Курганова

Koshel

2017

Int J of Chemical Kinetics

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This paper discusses the results of investigations on the kinetics of cumene oxidation to cumene hydroperoxide by molecular oxygen in the presence of N-hydroxyphthalimide as a catalyst. A mathematical model has been developed on the basis of the regularities of hydroperoxide and by-products formation. The model adequately describes changes in all reaction components in the course of the reaction. It has also been established that the role of N-hydroxyphthalimide in the process consists in the creation of a steady-state concentration of N-phthalimide radicals initiating oxidation by interacting with the hydrocarbon. C 2017

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