Electron spin resonance studies of oxidation. Part VIII. Elimination reactions of some hydroxyalkyl radicals

Buley, A. L.; Norman, R. O. C.; Pritchett, R. J.

doi:10.1039/j29660000849

Cited by 73 publications

(33 citation statements)

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“…Such a value for this rate constant is consistent with the unrearranged radical being the dominant species at high rates of initiation, as in the e.s.r. experiments (15,16), but the rearranged radical being dominant at low rates of initiation. If the rearrangement is also acid-catalyzed, [Ic], eq.…”

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Radiation-induced Rearrangement of Ethylene Glycol in Aqueous Solution

Burchill¹,

Perron²

1971

Can. J. Chem.

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Under y-irradiation, aqueous solutions of ethylene glycol containing hydrogen peroxide form acetaldehyde as a major product via a free-radical chain rearrangement. The yield of acetaldehyde is essentially unchanged when hydrogen peroxide is replaced by N 2 0 or HC104. A mechanism is proposed in which the glycol radical, ~H O H C H~O H , rearranges to the acetaldehyde precursor, c H 2 C H 0 , followed by the hydrogen atom transfer reaction; thus propagating a chain r e a~t i o n .~The rearrangement is also induced by the photo-dissociation of H 2 0 2 in aqueous solutions of ethylene glycol.Sous une y-irradiation, des solutions aqueuses d'ethylene glycol contenant du peroxyde d'hydrogene produisent de I'acCtaldChyde comme produit principal par une transposition radicalaire en chaine. Le rendement en adtaldChyde n'est pas modifiC lorsque le peroxyde d'hydrogtne est remplacC par N 2 0 ou HCIO.+. Un m h n i s m e est propose ou le radical glycol, cH0HCH2OH, se transpose en un prCcurseur, c H 2 C H 0 , de I'acetaldthyde suivi par une reaction de transfert d'atome d'hydrogene; il en rCsulte une rCaction de propagation en chaine.2 Dans des solutions aqueuses d'Cthylene glycol, la transposition peut Cgalement Ctre induite par la photo-dissociation de H202.

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“…The yield of acetaldehyde (G - 15) suggested that a chain reaction was involved but -it was the nature of this product which evoked our curiosity. Acetaldehyde cannot be represented as a product of the oxidation of ethylene glycol.…”

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Radiation-induced Rearrangement of Ethylene Glycol in Aqueous Solution

Burchill¹,

Perron²

1971

Can. J. Chem.

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“…It can be seen that there is very little difference between the slopes of the three lines but there is a significant change in the intercept. Even when radical-radical reaction [7] is omitted, the steady state method yields an extremely com- constant during the experiment, the expression simplifies to A plot of I/@,,, + us. 1/[Fe3 + ] (inset Fig.…”

Section: Results and Disc~ssisnmentioning

confidence: 99%

“…The O=CH-CH, radical would then abstract hydrogen from another ethylene glycol to produce acetaldehyde. Both these radicals have been shown to be present by electron spin resonance spectroscopy (7,8).…”

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The photolysis of hexaaquoiron(III) perchlorate in the presence of ethylene glycol

Carey¹,

Cosgrove²,

Oliver³

1977

Can. J. Chem.

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. Can. J. Chem. 55, 625 (1977). Two types of reactions occur when hexaaquoiron(II1) ion is irradiated at 254 nm in the presence of alcohols. Firstly, a charge transfer transition from a water centred orbital to an iron centred orbital produces OH' radicals which go on to abstract hydrogen from the alcohols. secondly ,!the reaction with the charge transfer excited states of iron(II1) species can lead to outer sphere oxidation of the alcohols. In this paper, these reactions have been studied in detail for the diol ethylene glycol in aqueous solutions. It has been found that the quantum yield of acetaldehyde, the major product of hydroxyl radical reactions with ethylene glycol, is 0.09 and the yield of formaldehyde, the major product of the direct charge transfer reaction, is 0.05 in 1 M ethylene glycol. The quantum yields for these major products, as well as minor products. such as glycolaldehyde and succinaldehyde, have been determined at several concentrations of ethylene glycol and iron. A detailed reaction scheme for the photolysis has been developed. JOHN H. CAREY, ERNEST G. COSGROVE et BARRY G. OLIVER. Can. J. Chem. 55, 625 (1977) I1 y a deux types de rCaction qui se produisent lorsque l'ion hexaaquofer(II1) est irradiC a 254 nm en presence d'alcools. En premier lieu, il y a une transition de transfert de charge a partir d'une orbitale centree au niveau de I'eau vers une orbitale centree sur le fer qui produit des radicaux O H qui ensuite enlevent de l'hydrogene des alcools. Deuxiemement il y a une reaction avec les Ctats excites de transfert de charge des espkces du fer(II1) qui peut conduire a des oxydations par les sphkres extCrieures de l'alcool. Dans la prCsente communication, on a Ctudit ces rkactions en detail pour le diol ethylene glycol en solution aqueuse. On a trouve que le rendement quantique d'acCtaldChyde, le produit majeur des reactions du radical hydroxyle avec l'ethylene glycol, est de 0.09 et le rendenlent de formaldehyde, qui est le produit majeur de la reaction de transfert directe de charge, est de 0.05 dans 1'6thyltne glycol 1 M. On a determine les rendements quantiques de ces produits majeurs ainsi que des produits mineurs tel que le glycolaldthyde et le succinaldthyde a plusieurs concentrations d'ethylene glycol et de fer. On a developpe un schema rtactionnel dttaillt pour la photolyse.[Traduit par le journal]

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“…It is proposed that the radical from propylene glycol is CH2COCH3 , and that by analogy, the triplet sp ectrum from ethylene glycol belon gs to th e radical CH2CHO. " Similar arguments have appeared recently [28,29]. Although a molecular orbital account will not be attempted, allylic resonance structure s can be written for the se radicals,…”

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confidence: 99%