Recent developments on the epoxidation of alkenes using hydrogen peroxide as an oxidant

Grigoropoulou, Georgia; Clark, James H.; Elings, Jacob A.

doi:10.1039/b208925b

Cited by 438 publications

(240 citation statements)

References 63 publications

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“…Metal-free epoxidation of alkenes with H 2 O 2 occurs in the presence of some auxiliaries (nitriles, carbodiimides, etc) which convert hydrogen peroxide to a more active oxidant. 9 On the other hand, halohydrins are widely used in epoxide synthesis in both laboratorial and industrial scale. 10 The cohalogenation 11 with water (halogenation of alkenes in aqueous solutions) is an effective way to prepare these intermediates.…”

Section: Introductionmentioning

confidence: 99%

A new environmental friendly clay catalyst for one-pot coiodination and epoxidation of alkenes

Bernini

Aguiar

2007

J. Braz. Chem. Soc.

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A argila comercial brasileira Bentonit Brasgel ® foi caracterizada por análises química e textural, DRX e RMN no estado sólido de 27 Al and 29 Si, que indicaram a presença de quartzo-α e esmectita como argilo-minerais. Essa argila se mostrou um catalisador eficiente para a conversão de alquenos nos respectivos epóxidos através da reação com iodo/água seguida de adição de KOH em hexano in situ (80-91 %). Resultados similares foram obtidos usando-se Bentonit Brasgel™ intercalada com Ag(I).The commercial Brazilian clay Bentonit Brasgel™ was characterized by chemical and textural analyses, XRD, and 27 Al and 29 Si MAS-NMR, that indicated the presence of α-quartz and smectite as clay-minerals. This natural clay proved to be an efficient catalyst for the conversion of alkenes into epoxides by the reaction with iodine/water followed by in situ addition of KOH in hexane (80-91 % yield). Similar results were obtained with Bentonit Brasgel™ intercalated with Ag(I). Keywords: epoxide, coiodination, iodohydrin, clay, alkenes IntroductionNowadays, the search for cleaner process is one of the major challenges in modern chemical industries. 1 Moreover, the high versatility, low-cost and gain in yield/ selectivity turn clays very attractive catalysts in the green chemistry point of view as they are reusable and present minimal environmental impact. 2 Within this context, the use of clays and clay-minerals in synthetic organic chemistry has increased enormously in the last years. 3 Epoxides are useful compounds in synthetic organic chemistry 3 and the interest for these valuable compounds has increased with the discovery of some biological activities related to the oxirane ring. 5 There are several efficient methodologies for the preparation of epoxides, for example: the oxidation of alkenes with peracids and the cyclization of halohydrins with bases are the most employed. 4 Peracids and analogues have been used to prepare epoxides; even though, these reagents must be carefully manipulated, due to their tendency to explosion. 6 The epoxidation of alkenes with molecular O 2 or H 2 O 2 seems to be very attractive, but it is expensive because it needs a metal-based catalytic system 7 or zeolites 8 and frequently suffers from formation of undesirable oxygenated by-products. Metal-free epoxidation of alkenes with H 2 O 2 occurs in the presence of some auxiliaries (nitriles, carbodiimides, etc) which convert hydrogen peroxide to a more active oxidant. 9 On the other hand, halohydrins are widely used in epoxide synthesis in both laboratorial and industrial scale. 10 The cohalogenation 11 with water (halogenation of alkenes in aqueous solutions) is an effective way to prepare these intermediates. 12 Although this methodology is effective, the handling and manipulation of toxic and corrosive halogens is problematic (especially in large-scale), then the search for alternative sources of electrophilic halogen is of great interest. 13 1510A New Environmentally Friendly Clay Catalyst for One-pot Coiodination J. Braz. Chem. Soc.Recently, we...

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Section: Introductionmentioning

confidence: 99%

A new environmental friendly clay catalyst for one-pot coiodination and epoxidation of alkenes

Bernini

Aguiar

2007

J. Braz. Chem. Soc.

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“…Under liquid-phase epoxidation, catalytically active metal complexes react with peroxides to atach the reactive oxygen as ligand which atack the double bond of olein. Hydrogen peroxide is efective oxygen donor and has an advantage of low-temperature reaction giving environmentally benign water as a by-product [61,62].…”

Section: Synthesis Of 34-epoxy-1-butene In Liquid Phasementioning

confidence: 99%

Reactivity of a Simplest Conjugated Diolefin in Liquid-Phase Oxidation: Mechanisms and Products

Кузнецова¹,

Кузнецова²,

Yakovina³

et al. 2018

Alkenes

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Ethylene is the simplest member of olein series, but butadiene-1,3 (BD) is the simplest conjugated diolein. In this chapter, we describe liquid-phase oxidations of BD with an emphasis on comparison of the diolein with monooleins. BD interacts with oxygen to form polyperoxide, whose thermal decomposition or hydrogenation leads to the formation of 2-butene-1,4-diol, 3-butene-1,2-diol, or butanediols together with furan and acrolein. BD can be oxidized in polar solvents by radical chain route to form directly the dioxygenates. Metal catalysts are able to control the oxidation by promoting formation of 2-butene-1,4-diol, 4-hydroxybut-2-enal, and furan. PdTe/C catalyst is applied in industry to produce 2-butene-1,4-diol diacetates with selectivity of 98%. The outstanding selectivity of the catalyst is caused by combined action of components in nonradical route and esteriication of inal product in acetic acid. Similar reaction in methyl alcohol yields 1,4-dimethoxy-2-butene, but with lower eiciency. The nonradical mechanism is irmly established for epoxidation of BD with hydrogen peroxide catalyzed by phosphotungstates. The selectivity of BD and hydrogen peroxide conversion to 3,4-epoxy-1-butene around 100% is atained. Analysis of published information and our own studies show many similarities in oxidation of BD and light oleins, which are very useful for understanding the mechanisms.

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“…Epoxides are highly useful intermediates for the production of a variety of important commercial products, 1,2 and therefore their synthesis is a subject of substantial academic and industrial interest. Olefin epoxidation is one of the main paths that lead to the production of epoxides both at a laboratory and at the industrial scale.…”

Section: Introductionmentioning

confidence: 99%

Light driven styrene epoxidation and hydrogen generation using H₂O as an oxygen source in a photoelectrosynthesis cell

et al. 2016

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Recent developments on the epoxidation of alkenes using hydrogen peroxide as an oxidant

Cited by 438 publications

References 63 publications

A new environmental friendly clay catalyst for one-pot coiodination and epoxidation of alkenes

A new environmental friendly clay catalyst for one-pot coiodination and epoxidation of alkenes

Reactivity of a Simplest Conjugated Diolefin in Liquid-Phase Oxidation: Mechanisms and Products

Light driven styrene epoxidation and hydrogen generation using H₂O as an oxygen source in a photoelectrosynthesis cell

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Recent developments on the epoxidation of alkenes using hydrogen peroxide as an oxidant

Cited by 438 publications

References 63 publications

A new environmental friendly clay catalyst for one-pot coiodination and epoxidation of alkenes

A new environmental friendly clay catalyst for one-pot coiodination and epoxidation of alkenes

Reactivity of a Simplest Conjugated Diolefin in Liquid-Phase Oxidation: Mechanisms and Products

Light driven styrene epoxidation and hydrogen generation using H2O as an oxygen source in a photoelectrosynthesis cell

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Light driven styrene epoxidation and hydrogen generation using H₂O as an oxygen source in a photoelectrosynthesis cell