OH radical oxidation of the sorbitylfurfural furanic ring to sugar derivatives induced by radiolysis in aerobic environment

Russo, Marialuisa; Poggi, Gabriella; Navacchia, Maria Luisa; D’Angelantonio, Mila; Emmi, Salvatore S.

doi:10.1163/156856706775372816

Cited by 2 publications

(9 citation statements)

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“…The reaction of OH with SF and with furfural, one of its components, was clarified in our recent papers [1,7], in connection with the effect of controlled amounts of oxygen added to produce peroxyl species [6]. Peroxyl radicals were proven to decay undergoing both an intra-and inter-molecular rearrangement.…”

Section: Methodsmentioning

confidence: 99%

“…Peroxyl radicals were proven to decay undergoing both an intra-and inter-molecular rearrangement. In fact, the peroxyl intermediates deriving from oxidation of the furanic ring undergo monoand/or bimolecular decay, because oxygen forms an adduct with the hydroxylated SF before and after its β-cleavage reaction [6,8].…”

Section: Methodsmentioning

confidence: 99%

“…This promising yield, with respect to possible use in organic synthesis [6], suggests that following a similar reaction path other products can be achieved simply by changing the furan ring substituents or the nature of the condensed sugar.…”

Section: Introductionmentioning

confidence: 95%

“…Pulses of high energy electrons or γ -rays combined with absorption detection allow to monitor the formation and decay and the transient species and the identification of the final products together with the consumption of the precursor [6]. Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

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A kinetic, spectral and theoretical investigation on the role of oxygen in the radiolytic oxidation of a sorbityl cyclic acetal

Poggi

D’Angelantonio

Russo

et al. 2008

Res. Chem. Intermed.

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Abstract-The oxidation process of the cyclic acetal sorbitylfurfural (SF) has been thoroughly examined from the kinetic, spectroscopic and theoretical point of view. Oxidation has been initiated by the radiolitically produced OH radical in the presence of variable oxygen amounts. Two competing reaction pathways are evidenced which lead to quite different products, although they do not affect the acetal ring integrity. The peroxidation of the hydroxylated furanic ring (k 4 = (6.1 ± 0.9) × 10 8 M −1 s −1 ) maintains the ring structure via HO • 2 elimination (k 6 = (1.9 ± 0.4) × 10 5 s −1 ). Unlike that, the peroxidation of the pseudo-allylic radical (k 5 = (1.9 ± 0.9) × 10 9 M −1 s −1 ), formed via β-cleavage, fixes the destructured intermediate, leading to a tetroxide, which slowly decomposes through a Russell mechanism (k 8 = (2.3 ± 0.6) × 10 2 s −1 ). It is confirmed that the steady state concentration of the tetroxide is very low, which suggests a molar absorption coefficient for it around 1.2 × 10 4 M −1 cm −1 at 265 nm. The end products of the latter pathway have been characterized as carboxylic and butenal D-sorbitol derivatives. The kinetic and spectral data of every step of the process have been fitted by the above outlined mechanism. The energetics of the mechanism has been detailed by ab initio computations as well, carrying further substantiation to it. Semi-empirical calculations were also employed to describe the spectral properties of each intermediate.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

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A kinetic, spectral and theoretical investigation on the role of oxygen in the radiolytic oxidation of a sorbityl cyclic acetal

Poggi

D’Angelantonio

Russo

et al. 2008

Res. Chem. Intermed.

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“…15 In the present paper, we describe the syntheses of 2,4-furfurylidene-D-sorbitol (1) and of the tetra-methyl ether 2. From our 500 MHz 1 H-and 13 C-NMR studies on the conformations of the cyclic acetals 1 and 2, a structure was proposed for both compounds. The structures were confirmed and interpreted by in silico studies based both on Density Functional Theory (DFT) and on classical molecular dynamics approaches.…”

Section: Introductionmentioning

confidence: 99%

2,4-Furfurylidene-D-sorbitol and its tetra-methyl ether: synthesis, conformational studies, and radical scavenging activity

Ciuffreda¹,

Brizzolari²,

Casati³

et al. 2016

Arkivoc

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The structure of 1-[2-(furan-2-yl)-5-hydroxy-6-(hydroxymethyl)-1,3-dioxan-4-yl]ethane-1,2-diol] (2,4-furfurylidene-D-sorbitol) and its tetra-methyl ether was established by a detailed NMR analysis. The conformational structure for both compounds was confirmed by in silico studies based both on Density Functional Theory (DFT) and on classical molecular dynamics approaches. The scavenging activity against hydroxyl radicals (•OH) of compounds was established by the 2-deoxyribose degradation assay.

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OH radical oxidation of the sorbitylfurfural furanic ring to sugar derivatives induced by radiolysis in aerobic environment

Cited by 2 publications

References 0 publications

A kinetic, spectral and theoretical investigation on the role of oxygen in the radiolytic oxidation of a sorbityl cyclic acetal

A kinetic, spectral and theoretical investigation on the role of oxygen in the radiolytic oxidation of a sorbityl cyclic acetal

2,4-Furfurylidene-D-sorbitol and its tetra-methyl ether: synthesis, conformational studies, and radical scavenging activity

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