Mechanistic insights in the olefin epoxidation with cyclohexyl hydroperoxide

Hereijgers, Bart P. C.; Parton, Rudy F.; Weckhuysen, Bert M.

doi:10.1039/c2cy00455k

Cited by 20 publications

(20 citation statements)

References 62 publications

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“…These results suggest a reaction mechanism similar to that reported by Tonigold et al, who investigated the selective oxidation of cyclohexene under solvent-free conditions . It is assumed that the remaining 23% of selectivity corresponds to the formation of higher molecular weight products, such as oligomers of cyclohexene . In comparison to Cu 3 (BTC) 2 the conversion of cyclohexene and TBHP over 1 Cu as well as the turnover frequency (TOF) are twice as high (Figure , Table ).…”

Section: Catalytic Activity Of 1 Cu and 1 Cosupporting

confidence: 82%

Bis(carboxyphenyl)-1,2,4-triazole Based Metal–Organic Frameworks: Impact of Metal Ion Substitution on Adsorption Performance

Kobalz

Möllmer

et al. 2016

Inorg. Chem.

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This work presents the syntheses and comprehensive characterization of six paddlewheel based metal− organic frameworks (MOFs) with the general formula ∞ 3 [M 2 L 2 ] (M = Cu, Co, Zn; L = bis(carboxyphenyl)-1,2,4-triazole) forming an isoreticular series with rutile (rtl) topology. These microporous materials are suitable for a systematic investigation of structure−property relationships based on the impact of the metal ion. Depending on the metal ion, the calculated porosities and the pore diameters reach from 58% to 61% and 300 to 750 pm, respectively. Simultaneous thermal analysis and temperature dependent PXRD studies reveal varying thermal behavior with stabilities up to 400°C. In the case of syntheses with various Co 2+ /Cu 2+ , Co 2+ /Zn 2+ , and Cu 2+ /Zn 2+ ratios, ICP-OES analyses and SEM-EDX studies confirm the formation of mixed metal MOFs and the metal ion distribution in the bulk samples as well as within the crystals. For the systematic investigation of CO 2 (298 K) and N 2 (77 K) adsorption properties, all materials were previously subjected to extraction with supercritical CO 2 . Depending on the metal ion, this procedure causes different phase transitions for each compound. As a result, adsorption studies reveal varying network flexibility for these MOFs. This study is one of the rare examples demonstrating that targeted modification of gate opening pressure, hysteresis shape, and adsorbed amounts of CO 2 or N 2 are possible by choice of the metal ion. This finding is supported by adsorption studies on the mixed metal MOF ∞ 3 [(Cu 0.48 Co 0.52 ) 2 (p-L) 2 )], showing CO 2 adsorption/desorption characteristics of both homonuclear copper and cobalt materials, whereas N 2 does not induce gate opening of the framework, as observed for the cobalt MOF. Furthermore, catalytic studies reveal that ∞ 3 [Cu 2 (p-L) 2 )] is a suitable catalyst for the oxidation of cyclohexene with tert-butylhydroperoxide (TBHP) with high conversion of the starting materials and good selectivity. Its robustness under the applied catalysis conditions leads to similar conversions in repetition measurements.

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Section: Catalytic Activity Of 1 Cu and 1 Cosupporting

confidence: 82%

Bis(carboxyphenyl)-1,2,4-triazole Based Metal–Organic Frameworks: Impact of Metal Ion Substitution on Adsorption Performance

Kobalz

Möllmer

et al. 2016

Inorg. Chem.

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“…As shown in Scheme 1 and reported by several authors, [35][36][37][38][39][40][41] the main oxidation products of cyclohexene are (I) cyclohexane oxide, (II) cyclohexane-1,2-diol, (III) 3-hydroperoxycyclohex-1-ene, (IV) cyclohexenol and (V) cyclohexenone. According to Weiner et al, selectivity of the above cited products varies with the catalyst, oxidant, temperature, time, pressure and solvent so on and so forth.…”

Section: Resultsmentioning

confidence: 68%

Highly efficient and expeditious PdO/SBA-15 catalysts for allylic oxidation of cyclohexene to cyclohexenone

Ganji

Bukya

Vakati

et al. 2013

Catal. Sci. Technol.

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A series of four PdO/SBA-15 catalysts with 1, 2, 4, 5% (by weight) loading of PdO have been prepared by a conventional impregnation method and are characterized by N 2 -adsorption, low-angle and wideangle XRD, XPS and TEM techniques. The catalysts exhibited very high conversion of cyclohexene and high selectivity of cyclohexenone with 70% t-BuOOH in CH 3 CN. The structural and textural characteristics of catalysts play a crucial role in high conversion and selectivity.

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“…Epoxidation of alkenes as a fundamental reaction in organic synthesis provides oxirane (epoxide) compounds that are considered as useful synthetic intermediates in the production of epoxy resins, perfumes, plasticizers, pharmaceuticals, cosmetics, etc. [1][2][3][4]; but their production involves high consumption of energy, lack of selectivity and environmental concerns [5,6]. So, finding a highly selective method is in demand for the preparation of such materials.…”

Section: Introductionmentioning

confidence: 99%

Selective and metal-free epoxidation of terminal alkenes by heterogeneous polydioxirane in mild conditions

et al. 2018

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Polydioxirane (PDOX) was prepared by the treatment of polysalicylaldehyde with Oxone and was found as a selective, highly efficient and heterogeneous reagent for epoxidation of alkenes which can be successfully isolated. This work also introduced a simpler, safer and milder way for epoxidation of alkenes with dioxirane groups than before. PDOX can be simply recovered from the reaction mixture by plain filtration and reused for eight runs without significant reactivity loss.

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Mechanistic insights in the olefin epoxidation with cyclohexyl hydroperoxide

Cited by 20 publications

References 62 publications

Bis(carboxyphenyl)-1,2,4-triazole Based Metal–Organic Frameworks: Impact of Metal Ion Substitution on Adsorption Performance

Bis(carboxyphenyl)-1,2,4-triazole Based Metal–Organic Frameworks: Impact of Metal Ion Substitution on Adsorption Performance

Highly efficient and expeditious PdO/SBA-15 catalysts for allylic oxidation of cyclohexene to cyclohexenone

Selective and metal-free epoxidation of terminal alkenes by heterogeneous polydioxirane in mild conditions

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