The catalytic oxidation of cyclohexanone to caprolactone using hexagonal mesoporous silica supported SbF3

Lambert, Arnold; Macquarrie, Duncan J.; Carr, Graham; Clark, James H.

doi:10.1039/b003161p

Cited by 27 publications

(20 citation statements)

References 4 publications

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“…We have found that by following a similar procedure to that found to be effective for the solid aluminum chloride catalysts, apparently stable forms of supported antimony trifluoride can be made. 31 Surface areas for these catalysts are generally excellent (300-∼1000 m 2 g -1 for some of the MTS-based materials). Thermal analysis shows that it is not made up of simple physisorbed SbF 3 .…”

Section: Other Covalently Bonded Lewis Acidsmentioning

confidence: 99%

Solid Acids for Green Chemistry

2002

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Solid acids and especially those based on micelle-templated silicas and other mesoporous high surface area support materials are beginning to play a significant role in the greening of fine and speciality chemicals manufacturing processes. A wide range of important organic reactions can be efficiently catalyzed by these materials, which can be designed to provide different types of acidity as well as high degrees of reaction selectivity. The solid acids generally have high turnover numbers and can be easily separated from the organic components. The combination of this chemistry with innovative reaction engineering offers exciting opportunities for innovative green chemical manufacturing in the future.

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Section: Other Covalently Bonded Lewis Acidsmentioning

confidence: 99%

Solid Acids for Green Chemistry

2002

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“…In the case of the silica gel materials, the product was identified by GCMS as caprolactone. The Baeyer Villiger reaction of cyclohexanone to produce caprolactone, particularly in the presence of Lewis acids, is a well known reaction and is the most likely mechanism for the formation of this product from the oxides supported on silica gel [11,12]. The ferrierite material produced the interesting product 3-methyl-1-pentanol, indicating the cleavage of the cyclohexane ring and subsequent oxidation of one of the carbons.…”

Section: Resultsmentioning

confidence: 99%

Oxidation of Cyclohexane by Transition Metal Oxides on Zeolites

Riley¹

2012

TOCATJ

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Transition metals (Co, Mn, Fe, and Cu) were deposited as the hydrated oxides on a series of zeolites (Y, , ZSM-5, mordenite, and ferrierite) and examined for activity for the oxidation of cyclohexane at 70°C and ambient pressure. The materials that demonstrated catalytic activity under these extremely mild conditions were the cobalt-based catalysts. The copper and copper/iron materials demonstrated stoichiometric activity for the oxidation of cyclohexane to cyclohexanol and cyclohexanone. The cobalt-based catalysts produced the intriguing products caprolactone, 1-hexanol, and 3-methyl-1-pentanol, as well as the expected cyclohexanol and cyclohexanone. Of most interest was the production of 1-hexanol, indicative of novel activity in the oxidative ring cleavage and oxidation of cyclohexane.

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“…Active heterogeneous catalysts for the BV oxidation of cycloalkanones with HP may be divided into four different classes: a) Brønsted-type acid catalysts, such as zeolites (H-b and USY), [4,5] alumina, [6] and polyoxometalates; [7] b) Lewistype acid catalysts, based on Sn IV (Sn-b, Sn-hydrotalcite, Snclay), [8][9][10][11][12]20] Sb V , [13,14] or supported Pt complexes; [2,15] c) basic oxides; [16,17] and d) catalysts based on elements that will allow the formation of MeÀOOH species, such as Ti IV incorporated into silicalite or b zeolite. [18,19] In general, catalysts belonging to classes a) and c) show limited preference for production of the lactone; this could be due either to subsequent lactone hydrolysis, possibly catalyzed by acid sites, or to the formation of unknown heavy compounds.…”

Section: Introductionmentioning

confidence: 99%

A Rationale of the Baeyer–Villiger Oxidation of Cyclohexanone to ε‐Caprolactone with Hydrogen Peroxide: Unprecedented Evidence for a Radical Mechanism Controlling Reactivity

Cavani

Raabová

Bigi

et al. 2010

Chemistry A European J

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We demonstrate, for the first time, in the Baeyer-Villiger oxidation of cyclohexanone with aqueous hydrogen peroxide under conditions aimed at obtaining ε-caprolactone, that a thermally activated radical reaction leads to the concurrent formation of adipic acid, even when a stoichiometric amount of the oxidant is used. In fact, ε-caprolactone is the primary reaction product, but it is more reactive than cyclohexanone, and quickly undergoes consecutive transformations. When titanium silicalite-1 (TS-1) is used as a catalyst, the high concentration of hydroxy radicals within its pores accelerates the reaction rates, and the consecutive formation of adipic acid (and of lighter diacids as well) becomes largely kinetically preferred. The proper choice of the solvent, which also may act as a radical scavenger, both without catalyst and with TS-1, is a powerful tool for controlling the rates of the various reactions involved.

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The catalytic oxidation of cyclohexanone to caprolactone using hexagonal mesoporous silica supported SbF3

Cited by 27 publications

References 4 publications

Solid Acids for Green Chemistry

Solid Acids for Green Chemistry

Oxidation of Cyclohexane by Transition Metal Oxides on Zeolites

A Rationale of the Baeyer–Villiger Oxidation of Cyclohexanone to ε‐Caprolactone with Hydrogen Peroxide: Unprecedented Evidence for a Radical Mechanism Controlling Reactivity

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