The Reaction of Di-t-butyl Peroxide and Benzaldehyde

Rust, Frederick F.; Seubold, Frank H.; Vaughan, William E.

doi:10.1021/ja01190a016

Cited by 37 publications

(18 citation statements)

References 2 publications

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“…Addition of the benzoyl radical to benzaldehyde was proposed as a key step in the reaction pathway. 317 However, the intermediacy of the benzoyloxybenzyl radical, proposed in this study, was not confirmed by a subsequent, related EPR study. 43 Urry and co-workers reported that irradiation of unsymmetrical vicinal triones induces the acyl exchange reaction (Scheme 174).…”

Section: Intermolecular Addition To Unsaturated Bonds Other Than Ccontrasting

confidence: 67%

“…In 1948, Rust and co-workers reported that the reaction of benzaldehyde and di- tert -butyl peroxide (130 °C, 30 h) yielded a mixture of meso and racemic 1,2-diphenylethylene glycol dibenzoate. Addition of the benzoyl radical to benzaldehyde was proposed as a key step in the reaction pathway . However, the intermediacy of the benzoyloxybenzyl radical, proposed in this study, was not confirmed by a subsequent, related EPR study …”

Section: Intermolecular Addition To Unsaturated Bonds Other Than C−c ...mentioning

confidence: 56%

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Chemistry of Acyl Radicals

et al. 1999

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Section: Intermolecular Addition To Unsaturated Bonds Other Than Ccontrasting

confidence: 67%

Section: Intermolecular Addition To Unsaturated Bonds Other Than C−c ...mentioning

confidence: 56%

Chemistry of Acyl Radicals

et al. 1999

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“…As early as 1948, the reaction of di-tert-butyl peroxide (DTBP) with benzaldehyde for the synthesis of diphenylethylene glycol dibenzoate was reported. [5] The reactionb etween benzaldehyde and DTBP at 130 8Cf or 30 ha fforded the desired product in 85 %y ield based on peroxidec onsumed [Eq. (1)].…”

Section: Acyl Radical Additionmentioning

confidence: 99%

Carbon‐Centered Radical Addition to C=X Bonds for C−X Bond Formation

Liu

Lei

2015

Chemistry An Asian Journal

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Among various kinds of radical reactions, the addition of carbon-centered radicals to unsaturated bonds represents a powerful tool for the construction of different C-C and C-X (X = N, O, S, etc.) bonds, in which typically applied unsaturated bonds include alkenes, alkynes, imines, carbonyls, and even thiocarbonyls. When C=X bonds are utilized as the radical acceptors, reactions usually occur at the carbon position to generate a heteroatom radical, during which C-C coupling products are formed. This reaction mode has dominated this field for several decades. However, there is also another unconventional type of radical addition mode, in which carbon-centered radicals attack the heteroatom position of C=X bonds to generate carbon radicals, during which selective C-X bond formation is achieved. This reaction mode demonstrates an effective method for the construction of different C-X bonds, such as C-O, C-N, and C-S bonds. This Focus Review gives an overview of recent advances in this unconventional field.

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“…The initially formed isatin ketyl-aldehyde acyl radical pair A (Scheme 2) is of triplet multiplicity, and escape out of cage is favored for these long-lived triplet radical pairs. [12] As electrophilic radicals, the acyl moieties have shown special ''oxygen-philic' reactivity in several reactions with aldehydes and ketones, [13] being apt to attack the carbonyl at the oxygen atom, resulting in homolytic cleavage of the Cϭ O bond, giving radical B (Scheme 2). This oxygen-philic reactivity of the acyl group toward the carbonyl oxygen atom in 1 can be best interpreted by inspection of the charge density distribution in the acyl radicals and in ground state 1, as shown in Figure 2.…”

Section: Resultsmentioning

confidence: 99%

“…[6b] This concept is a product of early studies on acyl 530 radical additions to aldehydes and ketones at the carbonyl oxygen, [13] in which the contribution of a polar transition state is postulated. SET from aliphatic acyl radical to highvalent metal cations such as Cu II , [14] Mn III , [15] Fe III [16] , Pb IV , [17] etc.…”

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confidence: 99%

Mechanism of Photoinduced Reactions between 1‐Acetylisatin and Aldehydes

et al. 2004

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Hydrogen atom abstraction from aliphatic (2a, 2b) and aromatic (2c, 2d, 2e) aldehydes by the triplet nπ* state of 1-acetylisatin (1) yielded triplet (isatin ketyl-aldehyde acyl) radical pairs, which follow an out-of-cage pathway in subsequent reactions to give a series of radical coupling products 4−7. This out-of-cage mechanism is supported by examination of the primary products at various degrees of conversions during the course of the reaction, by the results of addition reactions of thermally generated isatin acyl radical with neutral 1, and by calculation of the charge density distribution in the acyl radicals and in ground state 1. Therefore, the oxygen-philic attack of the acyl radical, which had escaped out of cage from the triplet radical pair, at the C(3) carbonyl oxygen atom of a ground state 1 selectively afforded the thermodynamically more stable addition radical B. The recombination of two radicals B gave the 3-indolinone dimers 4 and 5 as diastereomers, while coupling of B with the isatin ketyl furnished the dihydroisoindigo derivative 6. Isatide 7

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The Reaction of Di-t-butyl Peroxide and Benzaldehyde

Cited by 37 publications

References 2 publications

Chemistry of Acyl Radicals

Chemistry of Acyl Radicals

Carbon‐Centered Radical Addition to C=X Bonds for C−X Bond Formation

Mechanism of Photoinduced Reactions between 1‐Acetylisatin and Aldehydes

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