Metal‐Free: An Efficient and Selective Catalytic Aerobic Oxidation of Hydrocarbons with Oxime and <i>N</i>‐Hydroxyphthalimide

Zheng, Gengxiu; Liu, Chunhong; Wang, Qiufen; Wang, Mingyu; Yang, Ge

doi:10.1002/adsc.200900509

Cited by 57 publications

(37 citation statements)

References 28 publications

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“…[10] However, as mentioned before, in order to directly obtain the desired hydroperoxides, the presence of transition metal salts is generally detrimental. For this reason, in the last decade several procedures were reported for the aerobic oxidation of hydrocarbons using NHPI as organocatalyst in combination with initiators such as alkaline earth chlorides, [11] oximes, [12] quinones, [13] phenantrolines, [14] xanthones in combination with tetramethylammonium chloride, [15] quaternary ammonium bromides [16] and a,a-azobisisobutyronitrile. [17] Nevertheless, all these processes required relatively high temperatures (80 8C), affording the corresponding carbonylic and carboxylic derivatives as major products and no or limited amounts of hydroperoxides.…”

Section: Introductionmentioning

confidence: 99%

Hydroperoxidation of Tertiary Alkylaromatics Catalyzed By N‐Hydroxyphthalimide and Aldehydes under Mild Conditions

et al. 2011

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A metal-free catalytic system consisting of an aldehyde and N-hydroxyphthalimide (NHPI) for the selective oxidation of tertiary alkylaromatics with molecular oxygen has been developed. Cumene was oxidized efficiently to the corresponding hydroperoxide under mild conditions. The molecule-induced homolysis between peracids generated in situ and NHPI ensured the formation of the phthalimide N-oxyl (PINO) radical even at room temperature. Investigations on aldehyde, solvent and temperature effects allowed us to achieve good conversions with high selectivity in hydroperoxide. The optimized procedure was successfully extended to phenylcyclohexane, a valuable alternative for the production of phenol. The mechanism is discussed in detail

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Section: Introductionmentioning

confidence: 99%

Hydroperoxidation of Tertiary Alkylaromatics Catalyzed By N‐Hydroxyphthalimide and Aldehydes under Mild Conditions

et al. 2011

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“…Thus, the oxidation of toluene was examined by nonmetallic radical initiator. Unsatisfactorily, when dimethylglyoxime 6 and anthraquinone 17,18 were employed, the conversion with selectivity evidently declined (Run 8 and 9). And in the presence of the ABIN (Run 10), the reaction proceeded in much low conversion to result in lots of undesired products (BAl).…”

Section: Resultsmentioning

confidence: 99%

Remarkable Effect of PEG-1000-based Dicationic Ionic Liquid for N-hydroxyphthalimide-catalyzed Aerobic Selective Oxidation of Alkylaromatics

Lü¹,

Lu²,

Wang³

et al. 2012

Croat. Chem. Acta

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Abstract. PEG 1000-based functional dicationic acidic ionic liquid (PEG 1000 -DAIL) was used for the first time as the reaction solvent for the N-Hydroxyphthalimide (NHPI)-cobalt acetate(Co(OAc) 2 ) catalyzed aerobic oxidations of alkylaromatics to the corresponding acids. It enhanced the efficient catalytic ability of NHPI: 99.9 % conversion of toluene with 99.5 % selectivity for benzoic acid could be obtained at 80 °C in 10 h and ethylbenzene was selectively oxidized to benzoic acid. Several alkylaromatics were efficiently oxidized to their corresponding acids under mild conditions. For substituted toluene, the conversions of substrates and the selectivity of products was affected by the position and kind of substituted groups, respectively. Both the catalyst and PEG 1000 -DAIL could be reused at least eight times without significantly decreasing the catalytic activity.(doi: 10.5562/cca2051)

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“…Recently, we have found that at around 80 8C DH 2 could provide efficiently its corresponding N-oxyl radical for oxidation of hydrocarbons. [12] Therefore, it could be suggested that, in the present oxidation at higher temperatures above 70 8C, the formed N-oxyl radical of DH 2 tended to compete with dioxygen and TEMPO to participate in binding to cobaloxime, which limited the formation of the superoxo complex. So the oxidation became slower and gave lower conversions, as described in Figure 1.…”

Section: The Catalytic Mechanismmentioning

confidence: 97%

Activation of Dioxygen by Cobaloxime and Nitric Oxide for Efficient TEMPO‐Catalyzed Oxidation of Alcohols

et al. 2011

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The aerobic oxidation of alcohols to their corresponding carbonyl compounds could be efficiently accomplished by using the combination of cobalt nitrate, dimethylglyoxime and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) as a novel catalytic system, and various alcohols including primary and secondary benzylic, allylic and aliphatic alcohols could be quantitatively converted to the corresponding aldehydes or ketones at 70 8C under 0.4 MPa dioxygen pressure in dichloromethane. During the oxidation, the in situ generated cobaloxime and nitric oxide (NO) were responsible for the activation of dioxygen, respectively, thereby, two concerted catalytic routes exist: cobaloxime-activating-dioxygen TEMPO-catalyzed and NO-activating-dioxygen TEMPO-catalyzed aerobic oxidation of alcohols.

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Metal‐Free: An Efficient and Selective Catalytic Aerobic Oxidation of Hydrocarbons with Oxime and N‐Hydroxyphthalimide

Cited by 57 publications

References 28 publications

Hydroperoxidation of Tertiary Alkylaromatics Catalyzed By N‐Hydroxyphthalimide and Aldehydes under Mild Conditions

Hydroperoxidation of Tertiary Alkylaromatics Catalyzed By N‐Hydroxyphthalimide and Aldehydes under Mild Conditions

Remarkable Effect of PEG-1000-based Dicationic Ionic Liquid for N-hydroxyphthalimide-catalyzed Aerobic Selective Oxidation of Alkylaromatics

Activation of Dioxygen by Cobaloxime and Nitric Oxide for Efficient TEMPO‐Catalyzed Oxidation of Alcohols

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