Peroxides and peroxide-forming compounds

Clark, Donald R.

doi:10.1016/s1074-9098(01)00247-7

Cited by 101 publications

(79 citation statements)

References 3 publications

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“…28 In fact, when H 2 O 2 was used as the oxidant instead of O 2 , a substantial increase in yields was observed (entries 9–12, Figure 3). When the H 2 O 2 concentration was increased to 15 mM, the observed yield surpassed the 50% threshold (entry 11, 53%).…”

Section: Resultsmentioning

confidence: 97%

Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp³ C–H Bonds

et al. 2017

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The use of copper in directed C−H oxidation has been relatively underexplored. In a seminal example, Schönecker showed that copper and O2 promoted the hydroxylation of steroid-containing ligands. Recently, Baran (J. Am. Chem. Soc. 2015, 137, 13776) improved the reaction conditions to oxidize similar substrates with excellent yields. In both reports, the involvement of Cu2O2 intermediates was suggested. In this collaborative article, we studied the hydroxylation mechanism in great detail, resulting in the overhaul of the previously accepted mechanism and the development of improved reaction conditions. Extensive experimental evidence (spectroscopic characterization, kinetic analysis, intermolecular reactivity, and radical trap experiments) is provided to support each of the elementary steps proposed and the hypothesis that a key mononuclear LCuII(OOR) intermediate undergoes homolytic O−O cleavage to generate reactive RO• species, which are responsible for key C−H hydroxylation within the solvent cage. These key findings allowed the oxidation protocol to be reformulated, leading to improvements of the reaction cost, practicability, and isolated yield.

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Section: Resultsmentioning

confidence: 97%

Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp³ C–H Bonds

et al. 2017

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“…However, THF-containing solvent-pairs shown in Figure 1 may have safety issues when used on a practical scale due to possible formation of peroxides associated with handling THF. 50 The importance of the solvent characteristics has great impact on the greenness of a chemical process. 10,13,21,22 In this work, we consider the following solvent-pairs that consist of the combination of a hydrogen bond donor solvent and a hydrogen bond acceptor solvent as follows: (i) methanol−cyclohexanone (CHN); (ii) methanol−cyclopentanone (CPN); (iii) methanol−ethyl acetate (EtAc); (iv) methanol−γ-valerolactone (GVL); (v) methanol−γ-butyrolactone (GBL); (vi) ethanol−CHN; (vii) ethanol−CPN; (viii) ethanol−GVL; (ix) ethanol−GBL; (x) water−GVL; (xi) water−GBL.…”

Section: ■ Introductionmentioning

confidence: 99%

Replacement of Hazardous Chemicals Used in Engineering Plastics with Safe and Renewable Hydrogen-Bond Donor and Acceptor Solvent-Pair Mixtures

Duereh

Satō

Smith

et al. 2015

ACS Sustainable Chem. Eng.

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Mixtures of safe and renewable solvents can replace hazardous solvents presently being used in the manufacture of engineering plastics. In this work, a methodology is proposed for identifying solvent-pair mixtures for preparing polymer precursors, with poly(amic acid) (PAA) being studied as an example. The methodology uses a chemical safety index, Hansen solubility parameters and Kamlet−Taft solvatochromic parameters of the pure and solvent-pair mixtures to identify hydrogen bond acceptor (HBA)−hydrogen bond donor (HBD) solvent-pair combinations. Ten replacement solvent-pairs for PAA syntheses identified were cyclohexanone−methanol, cyclohexanone−ethanol, cyclopentanone−methanol, cyclopentanone−ethanol, γ-butyrolactone−methanol, γ-butyrolactone− ethanol, γ-butyrolactone−water, γ-valerolactone−methanol, γ-valerolactone−ethanol, and γ-valerolactone−water. Homogeneous PAA solutions could be obtained from HBA−HBD solvent-pair mixtures when their solubility parameters were within 21−29 MPa 0.5 and their Kamlet−Taft solvatochromic parameters were π* (>0.67) and β (>0.67) for nonaqueous solutions and π* (>0.68) and β (>0.59) for aqueous solutions. Replacement solvent-pairs, γ-valerolactone−ethanol, γ-valerolactone−water, and γ-butyrolactone−water gave homogeneous precursor solutions that were comparable with commercial solutions prepared with Nmethyl-2-pyrrolidone. The proposed methodology and reported solvatochromic parameters make it is possible to identify other solvent-pair mixtures and new solvent-pairs for preparing polymer precursor solutions used in engineering plastics.

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“…This chemical mechanism is also for alcohol because alcohol is one of peroxide forming compounds [23] X. Discussion X.1.…”

Section: Roch3 + O2 → Roch2ooh (Hydroperoxide) --------------Equationmentioning

confidence: 98%

“…X.6.The formation of peroxide in methyl ether and methanol is very rear because the peroxides formed from diethyl ether and higher. And from propel alcohol and higher molecular Wight [23]. To explain this phenomenon, we may say that BA in solvent contains electron rich atom with high electronagativty under goes free radical reaction slowly to form benzoic hydro peroxide.Then slowly react with another BA molecule to form BPO.…”

Section: Roch3 + O2 → Roch2ooh (Hydroperoxide) --------------Equationmentioning

confidence: 99%

An isocratic normal-phase high-performance liquid chromatographic method for the simultaneous determination of benzoyl peroxide and benzoic acid in one pharmaceutical preparation and their stability in different solvents

Hamdu¹

2014

IOSRJPBS

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Peroxides and peroxide-forming compounds

Cited by 101 publications

References 3 publications

Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp³ C–H Bonds

Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp³ C–H Bonds

Replacement of Hazardous Chemicals Used in Engineering Plastics with Safe and Renewable Hydrogen-Bond Donor and Acceptor Solvent-Pair Mixtures

An isocratic normal-phase high-performance liquid chromatographic method for the simultaneous determination of benzoyl peroxide and benzoic acid in one pharmaceutical preparation and their stability in different solvents

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Peroxides and peroxide-forming compounds

Cited by 101 publications

References 3 publications

Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp3 C–H Bonds

Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp3 C–H Bonds

Replacement of Hazardous Chemicals Used in Engineering Plastics with Safe and Renewable Hydrogen-Bond Donor and Acceptor Solvent-Pair Mixtures

An isocratic normal-phase high-performance liquid chromatographic method for the simultaneous determination of benzoyl peroxide and benzoic acid in one pharmaceutical preparation and their stability in different solvents

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Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp³ C–H Bonds

Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp³ C–H Bonds