ChemInform Abstract: REAKTIVITAET SUBSTITUIERTER BENZOLE, FURANE UND PYRIDINE GEGENUEBER HYDROXYLRADIKALEN

Savel'eva, O. S.; Shevchuk, L. G.; Vysotskaya, N. A.

doi:10.1002/chin.197327147

Cited by 2 publications

(5 citation statements)

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“…As expected, − attack in position 5 ( IA-5) , producing a resonant allylic radical on carbons C2, C3, and C4 (see Chart ), turns out to be more exothermic than any other path by 14 kcal/mol. The spectral data are also reported in Table .…”

Section: Resultssupporting

confidence: 70%

“…About the possible attack paths, dealing with aliphatic − and aromatic , aldehydes and furanic − , compounds, the literature reports three possible routes which, in the order, can produce either an adduct radical, an acylic radical, or a radical cation.…”

Section: Resultsmentioning

confidence: 99%

“…A similar mechanism had been proposed previously by Lilie 4 in a pulse radiolysis study of furan in aqueous alkaline solution. A few kinetic data from competitive methods were reported by Savel'eva 5 and Vysotskaya 6 on γ-radiolysis, but no characterization of the processes and of the transients involved was given. The nature and destiny of the intermediates formed upon reaction of OH with furfural is the subject of the present paper.…”

Section: Introductionmentioning

confidence: 99%

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Reaction of the OH Radical with Furfural. Spectral and Kinetic Investigation by Pulse Radiolysis and by ab Initio and Semiempirical Methods

et al. 1999

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The reaction between the OH radical and furfural and the first stages of the subsequent processes have been investigated in detail. The model proposed for the overall kinetics has been verified by means of linear and nonlinear fittings up to the millisecond range. The identification of the intermediates has been based on ab initio optimized production enthalpies, as well as on the comparison of semiempirically predicted electronic transitions with the spectra observed after pulse radiolysis. The radical attack produces a radical adduct to the ring in position 5, k = (4.7 ± 0.8) × 109 M-1 s-1, which in sequence undergoes first a β-cleavage, k = (4.7 ± 2.4) × 105 s-1, and then a 1−6 hydrogen transfer, k = (3.4 ± 1.3) × 104 s-1. The final decay to a very low absorbing molecule occurs through a second-order reaction, k = (3.0 ± 0.5) × 108 M-1 s-1.

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Section: Resultssupporting

confidence: 70%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Reaction of the OH Radical with Furfural. Spectral and Kinetic Investigation by Pulse Radiolysis and by ab Initio and Semiempirical Methods

et al. 1999

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“…In the past furfural, together with furan, was the subject of a limited number of attempts to gather information on the nature and mechanistic behavior of the radical intermediates. Two of them concluded that OH addition is followed by the opening of the furanic ring. , Other two papers reported few kinetic data from competitive methods on the same process. , In a previous paper 16 we tried to clarify the course of OH attack to furfural, both by spectroscopic-kinetic pulse radiolysis and by calculating the energetics of the various steps. A preferential addition to C5 on the furanic ring, and the opening of the ring were found consistent with an overall mechanistic model, in which a fundamental role is played by a hydrogen shift between the two tails of the open ring itself.…”

Section: Introductionmentioning

confidence: 99%

“…12,13 Other two papers reported few kinetic data from competitive methods on the same process. 14,15 In a previous paper 16 we tried to clarify the course of OH attack to furfural, both by spectroscopic-kinetic pulse radiolysis and by calculating the energetics of the various steps. A preferential addition to C5 on the furanic ring, and the opening of the ring were found consistent with an overall mechanistic model, in which a fundamental role is played by a hydrogen shift between the two tails of the open ring itself.…”

Section: Introductionmentioning

confidence: 99%

The Selective OH Radical Oxidation of Sorbitylfurfural: A Combined Experimental and Theoretical Study

Emmi¹,

D’Angelantonio²,

Poggi³

et al. 2002

J. Phys. Chem. A

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Sorbitylfurfural (Furalglucitol), widely used in the cosmetic industry as antioxidant and antiinflammatory agent, reacts with hydroxyl radical in neutral aqueous solution with a rate constant almost at the diffusional limit, k 1 = 7.3 × 109 M-1 s-1. Despite the unselective character of the OH radical, addition to the 5‘ position in the furanic ring seems to provide the dominant path. The consequent allylic radical undergoes the cleavage of the C−O bond (k 2 = 1.7 × 106 s-1) in β position to form a pseudo-seven-atom ring via a hydrogen bond between the attacking OH group and the furanic oxygen. A 1,6 H-shift between the two oxygen atoms (k3 = 1.4 × 105 s-1) then precedes a disproportionation reaction which leads to the final products (k4 = 2.0 × 107 M-1 s-1). The proposed mechanism is based on the UV−vis spectra of intermediates and final products obtained after pulse and gamma radiolysis, on nonlinear kinetic fittings of absorbance versus time curves, on quantum-mechanical calculations of electronic transitions and reaction enthalpies. The two most important final products have been isolated and characterized as sorbityl-but-2-enal derivatives by LC-MS.

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ChemInform Abstract: REAKTIVITAET SUBSTITUIERTER BENZOLE, FURANE UND PYRIDINE GEGENUEBER HYDROXYLRADIKALEN

Cited by 2 publications

References 0 publications

Reaction of the OH Radical with Furfural. Spectral and Kinetic Investigation by Pulse Radiolysis and by ab Initio and Semiempirical Methods

Reaction of the OH Radical with Furfural. Spectral and Kinetic Investigation by Pulse Radiolysis and by ab Initio and Semiempirical Methods

The Selective OH Radical Oxidation of Sorbitylfurfural: A Combined Experimental and Theoretical Study

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