The functionalization of saturated hydrocarbons part XXIX. Application of tert-butyl hydroperoxide and dioxygen using soluble Fe(III) and Cu(II) chelates.

Barton, Derek H. R.; Bévière, Stéphane D.; Hill, David R.

doi:10.1016/s0040-4020(01)86982-9

Cited by 29 publications

(9 citation statements)

References 12 publications

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“…The amination of C–H bonds provides a route to N -alkyl and N -aryl amine derivatives that avoids typical functional group interconversions and reactants containing a functional group already present at the position where a C–N bond is desired. Intermolecular reactions that convert unactivated C–H bonds to C–N bonds are particularly challenging to achieve, but such reactions could directly modify complex molecules, create chemical feedstocks, or create functionalized polymers. , Methods for the oxidation of alkanes by the combination of peroxides and iron complexes have been developed, − but intermolecular functionalization of purely unactivated C–H bonds with reagents that form products containing common nitrogen-based functionality are rare . Most intermolecular amidations of C–H bonds have been catalyzed by copper complexes and occur at benzylic or allylic positions.…”

Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

et al. 2014

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We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C–H bonds over tertiary C–H bonds and even occur at primary C–H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 °C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO)2 at 100 °C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C–H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C–H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product.

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Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

et al. 2014

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“…Cyclohexane oxidation using Barton's GoAgg II system and H 2 O 2 as the oxidant in an inert atmosphere gives 91% efficiency (number of moles of oxidized products per mole of peroxide consumed) and a selectivity of 94% for III and 6% for II after 10 h. 233 Using Gif chemistry, saturated hydrocarbons were selectively transformed into ketones/alcohols and alkenes by application of dioxygen and t-BHP using soluble Fe(III) and Cu(II) chelates. 324 Cyclohexane hThe s been converted to cyclohexane carboxylic acid using Gif chemistry with Fe(CO) 5 and H 2 O 2 . 74 Gif and GoAgg oxidations are not important to industry.…”

Section: Direct One-step Conversion Of Cyclohexane To Adipic Acidmentioning

confidence: 99%

“…Solvent-free systems for functionalization of saturated hydrocarbons, operating with cyclohexane-soluble Fe(III) and Cu(II) catalysts, or catalysts in suspension using t-BHP and O 2 were first investigated by Barton et al 324 and later also by Schuchardt et al 325 The systems based on iron are more selective for oxygenated products. The presence of t-BHP as an initiator is fundamental for the reactivation of the system.…”

Section: Direct One-step Conversion Of Cyclohexane To Adipic Acidmentioning

confidence: 99%

Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum-Based Processes

Bart

Cavallaro

2014

Ind. Eng. Chem. Res.

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Adipic acid, which is a very important commodity chemical, is traditionally manufactured industrially by an aged and unsustainable multistep process that involves homogeneous catalysts, aggressive oxidants (concentrated nitric acid) and the production of large quantities of the greenhouse gas nitrous oxide. Much research and development into alternative and cleaner process routes to adipic acid have been carried out over the past 70 years. Improved reaction schemes have invoked variations in fossil raw materials (from benzene and phenol to cyclohexane, cyclohexanol, cyclohexanone, cyclohexene, butadiene, and adiponitrile, etc.), oxidants (O 2 , air, H 2 O 2 , t-BuOOH, ozone), catalysts (homogeneous, heterogeneous, phase transfer, biomimetic) and reaction conditions (low temperature, atmospheric pressure, and solvent-, metal-, halide-, and corrosion-free). No single proposed alternative pathwaysome of which are purely academicsimultaneously addresses the problems of petrochemical origin, toxic starting materials or reagents, generation of environmentally incompatible byproducts, use of forcing reaction conditions, and cost in an entirely satisfactory manner, despite very intense efforts. Recently, more benign bio-based reaction pathways have been proposed starting from renewables, such as glucose or vegetable oils (which will be discussed in Part 2 of this series).

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“…Catalytic liquid phase oxidation of cyclohexane by oxygen in the absence of solvents and additives is the most attractive. Although great efforts have been made to this reaction, it continues to be a challenge [3][4][5][6][7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

An Efficient and Reusable Catalyst of Bismuth-Containing SBA-15 Mesoporous Materials for Solvent-free Liquid Phase Oxidation of Cyclohexane by Oxygen

Wang

Zheng

et al. 2008

Catal Lett

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Bismuth-containing SBA-15 mesoporous materials with different n si /n Bi ratio was synthesized for the first time through a direct hydrothermal method, and characterized by various physico-chemical techniques. XRD patterns indicate that the synthesized materials have an ordered two-dimensional p6mm hexagonal mesostructure. Transmission electron microscopy and scanning electron microscopy studies show that Bi-SBA-15 has well-ordered hexagonal arrays of mesoporous channels and the morphology of rod-like particles. Raman spectroscopy and UV-Vis DRS show that bismuth atoms in Bi-SBA-15 exist in a highly dispersed state, and locate mainly at tetrahedrally coordinated sites. Thermogravimetric analysis was used to observe the removal of the organic template P 123 . In the catalytic test, Bi-SBA-15 is found to be a very efficient and reusable catalyst for the oxidation of cyclohexane, in a solvent-free system, with oxygen as oxidant. The influence of different parameters, such as reaction time, reaction temperature, oxygen pressure, and the dosage of catalyst on the oxidation of cyclohexane, is also investigated.

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The functionalization of saturated hydrocarbons part XXIX. Application of tert-butyl hydroperoxide and dioxygen using soluble Fe(III) and Cu(II) chelates.

Cited by 29 publications

References 12 publications

Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum-Based Processes

An Efficient and Reusable Catalyst of Bismuth-Containing SBA-15 Mesoporous Materials for Solvent-free Liquid Phase Oxidation of Cyclohexane by Oxygen

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