Hydrocarbon radical cations

Courtneidge, John L.; Davies, Alwyn G.

doi:10.1021/ar00135a003

Cited by 77 publications

(17 citation statements)

References 38 publications

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“…This reaction is similar to that with non-fluorinated benzoyl peroxides, l4 and the debutylated product 6 was isolated as the predominant product [see equation ( 5 ) ] . Therefore, this system can be used as one of the model systems for studying the fragmentation patterns of 1 + ' and other related radical cations.…”

Section: Oxidation Of 1 By (C6f5c02)z In F113mentioning

confidence: 65%

“…We now turn our attention to some other observations. (1) Although from the acceptor (CsFsC02)~ the debutylated product 6 is the main product (87%) and the undebutylated product 9 is formed only in trace amounts [equation ( 5 ) ] , this state of affairs is completely reversed when (n-C3F,C02)2 is the acceptor, i.e. the undebutylated product 11 (44%) rather than the debutylated product 12 (30%) becomes the more abundant [equation ( 6 ) ] .…”

Section: Oxidation Of 1 By (C6f5c02)z In F113mentioning

confidence: 99%

“…the undebutylated product 11 (44%) rather than the debutylated product 12 (30%) becomes the more abundant [equation ( 6 ) ] . (2) The demethylated quinone product is also formed [equation ( 5 ) ] , albeit only in small amounts, in F113. These observations might be rationalized by alternative reaction pathways for CP-I1 in Scheme 2 , i.e.…”

Section: Oxidation Of 1 By (C6f5c02)z In F113mentioning

confidence: 99%

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Reactivity and reaction patterns of alkyl alkoxybenzene radical cations. Mechanistic pathways of the reactions between 2,5‐DI‐tert‐Butyl‐1, 4‐Dimethoxybenzene and perfluorodiacyl peroxides

Jiang¹,

Zhao²,

Gong³

1991

J of Physical Organic Chem

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In the reactions of 2,5‐di‐tert‐butyl‐1,4‐dimethoxybezene (1) with different oxidants, the radical cation 1+. is always detectable by EPR. However, the observed reactivity of 1+. depends greatly on the oxidation systems employed. In S2O 82−Cu2+HOAc and Ce4+HOAc systems (HOAc = acetic acid), 1+. appears to have long lifetimes and does not undergo fragmentation spontaneously. In contrast, in (RFCO2)2CF2CICFCI2 (F113) systems, the readily formed 1+. is short‐lived, and large amounts of de‐tert‐butylation products have been isolated. Experimental results imply that the CC bond cleavage involved in de‐tert‐butylation could be a consequence of an attack by perfluoroacyloxy radical on 1+. in their original solvent cage. The fact that addition of methanol to the reaction mixture leads to the formation of a large amount of tBuOCH3 (46%) and other evidence suggest that the tert‐butyl group leaves as a carbocation. On the basis of these results, we conclude that the reactions of 1 with (RFCO2)2 are initiated by electron transfer and followed by a fast coupling of various radical species, namely, 1+. with RFCO2 or with RF in the solvent cage, to form σ‐complexes which collapse or react with nucleophiles to yield the final products.

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Section: Oxidation Of 1 By (C6f5c02)z In F113mentioning

confidence: 65%

Section: Oxidation Of 1 By (C6f5c02)z In F113mentioning

confidence: 99%

Section: Oxidation Of 1 By (C6f5c02)z In F113mentioning

confidence: 99%

See 1 more Smart Citation

Reactivity and reaction patterns of alkyl alkoxybenzene radical cations. Mechanistic pathways of the reactions between 2,5‐DI‐tert‐Butyl‐1, 4‐Dimethoxybenzene and perfluorodiacyl peroxides

Jiang¹,

Zhao²,

Gong³

1991

J of Physical Organic Chem

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“…spectroscopy. 1 In particular, in the context of the present paper, we have shown that the radical cations (Ig+) of various alkylcyclopentadienes can be identified when the parent hydrocarbons (I; X = CR2) are photolysed in trifluoroacetic acid solution.2.3…”

mentioning

confidence: 70%

The electron spin resonance spectra of the radical cations of furans, thiophenes, and pyrroles in liquid solution

Davies¹,

Juliá²,

Yazdi³

1987

J. Chem. Soc., Chem. Commun.

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“…In particular, A1C1 3 in dichloromethane proved to be the system of choice for hydrocarbons (61), thiaheterocycles (62), and organosilicon compounds (63), while tris(pbromophenyl)ammoniumyl hexa-chloroantimonate in this solvent was more appropriate for some nitrogen-containing compounds (64). UV-irradiation enhances the oxidizing power of various reagents, so that derivatives of benzene (65) and polyenes (66), as well as those of azulene (67) and cyclooctatetraene (68) could be converted to their radical cations. Oxidation of the parent azulene and cyclooctatetraene required the use of a rapid flow system (58), while unsubstituted benzene and polyenes had to undergo more rigorous treatments indicated below.…”

Section: Radical Cationsmentioning

confidence: 99%

Organic Radical Ions as Studied by Epr Spectroscopy

Gerson¹

1998

Foundations of Modern EPR

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Hydrocarbon radical cations

Cited by 77 publications

References 38 publications

Reactivity and reaction patterns of alkyl alkoxybenzene radical cations. Mechanistic pathways of the reactions between 2,5‐DI‐tert‐Butyl‐1, 4‐Dimethoxybenzene and perfluorodiacyl peroxides

Reactivity and reaction patterns of alkyl alkoxybenzene radical cations. Mechanistic pathways of the reactions between 2,5‐DI‐tert‐Butyl‐1, 4‐Dimethoxybenzene and perfluorodiacyl peroxides

The electron spin resonance spectra of the radical cations of furans, thiophenes, and pyrroles in liquid solution

Organic Radical Ions as Studied by Epr Spectroscopy

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