Zur isomerisierung von cyclohexyl-/ methylcyclopentylkationen in der gasphase

Wesdemiotis, Chrysostomos; Wolfschütz, Roland; Schwarz, Helmut

doi:10.1016/0040-4020(80)80015-9

Cited by 31 publications

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References 22 publications

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“…Instead, the formal abstraction of two hydrogen atoms likely occurs by hydride abstraction by C2 of 12 to yield 25 (Scheme 3), followed by proton transfer from the methylcyclopentyl cation, a rearrangement product of the initially formed cyclohexyl cation. 14 In conclusion, the 2,4,6-tridehydropyridine radical cation 12 was successfully generated. The first bond formation in 12 occurs at C2 via nucleophilic addition, which quenches the C− N ortho-benzyne moiety.…”

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confidence: 80%

“…Further, hydride abstraction is the major reaction for 12 upon interaction with cyclohexane (as well as for 14 – 17 ; Table ). Instead, the formal abstraction of two hydrogen atoms likely occurs by hydride abstraction by C2 of 12 to yield 25 (Scheme ), followed by proton transfer from the methylcyclopentyl cation, a rearrangement product of the initially formed cyclohexyl cation …”

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confidence: 99%

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Reactivity of a σ,σ,σ,σ-Tetraradical: The 2,4,6-Tridehydropyridine Radical Cation

et al. 2012

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The 2,4,6-tridehydropyridine radical cation, an analogue of the elusive 1,2,3,5-tetradehydrobenzene, was generated in the gas phase and its reactivity examined. Surprisingly, the tetraradical was found not to undergo radical reactions. This behavior is rationalized by resonance structures hindering fast radical reactions. This makes the cation highly electrophilic, and it rapidly reacts with many nucleophiles by quenching the N-C ortho-benzyne moiety, thereby generating a relatively unreactive meta-benzyne analogue.

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confidence: 80%

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confidence: 99%

Reactivity of a σ,σ,σ,σ-Tetraradical: The 2,4,6-Tridehydropyridine Radical Cation

et al. 2012

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Mass Spectra of Double‐Bonded Groups

Gäumann

2009

Patai's Chemistry of Functional Groups

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An Introduction, to Warm Up The Localization of the C  C Double Bond: an Analytical Problem Ethylene: An Old Faithful The Pentene Story Heptene: The Other Story Alkenes: To Fill Some Gaps Acetone, Seemingly Simple Other Ketones: The More it Changes, the More It Is the Same Diels–Alder and Retro‐Diels–Alder Reactions Acknowledgments

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Zur Kohlenstoff‐Äquilibrierung in cyclischen C₆H‐Kationen in der Gasphase und zum Mechanismus der unimolekularen Ethylen‐Abspaltung

et al. 1981

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Die Untersuchung von sechs doppelt "C-markierten C,H,,X-Derivaten. 6 a -9 , (X = CO,H, Br) und einer [D,] und nicht die von 10. Ein Vergleich der MNDO-und MIND0/3-Rechenverfahren ergibt im Hinblick auf einige relevante strukturelle und energetische Aspekte von pyramidalen Kationen, da0 MNDO generell die Bildungsenthalpie solcher nicht-klassischer lonen zu hoch berechnet, wahrend MIND013 den Cyclopropyl-Kation-Charakter dieser lonen entschieden zu stark bewertet. Die Synthesen der I3C,-markierten Verbindungen werden beschrieben. On the Carbon Equilibration of Cyclic C,H;, Cations in the Gas Phase and the Mechanism of Unimolecular Ethylene EliminationThe investigation of six '3C2-labelled (6a -9) and one [D,]-labelled (18) precursors unambiguOudy demonstrates, that unimolecular ethylene elimination from the metastable gaseous C,HA cations generated from the above mentioned compounds by dissociative ionization is preceded by both complete carbon and hydrogen scrambling. Whereas the scrambling can involve various intermediates, e.g. 3,4, and 5, MNDO calculations indicate that the minimal energy reaction path (MERP) for loss of C,H, from C,HA proceeds via the transition state 15, which is 11 kcal . mol-' lower in energy than the isomeric structure 16. 15, which can be viewed as a partially opened cydopropyl cation ,,solvated" by interaction with C2H,, decomposes to C2H, and C,H; which in agreement with experimental results has the structure of I-methylallyl cation (11) and not that of the isomeric 2-methylallyl cation (10). A brief comparison is made for the MIND013 and MNDO procedures in computing both structural and energetic features of pyramidal carbocations. The results indicate that MNDO overestimates substantially the heats of formations of such nonclassical cations, whereas MIND013 considerably overestimates the cyclopropyl cation ,,character" of the structures investigated. The syntheses of the ''C2-labeIled compounds are described.

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Zur isomerisierung von cyclohexyl-/ methylcyclopentylkationen in der gasphase

Cited by 31 publications

References 22 publications

Reactivity of a σ,σ,σ,σ-Tetraradical: The 2,4,6-Tridehydropyridine Radical Cation

Reactivity of a σ,σ,σ,σ-Tetraradical: The 2,4,6-Tridehydropyridine Radical Cation

Mass Spectra of Double‐Bonded Groups

Zur Kohlenstoff‐Äquilibrierung in cyclischen C₆H‐Kationen in der Gasphase und zum Mechanismus der unimolekularen Ethylen‐Abspaltung

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Zur isomerisierung von cyclohexyl-/ methylcyclopentylkationen in der gasphase

Cited by 31 publications

References 22 publications

Reactivity of a σ,σ,σ,σ-Tetraradical: The 2,4,6-Tridehydropyridine Radical Cation

Reactivity of a σ,σ,σ,σ-Tetraradical: The 2,4,6-Tridehydropyridine Radical Cation

Mass Spectra of Double‐Bonded Groups

Zur Kohlenstoff‐Äquilibrierung in cyclischen C6H‐Kationen in der Gasphase und zum Mechanismus der unimolekularen Ethylen‐Abspaltung

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Zur Kohlenstoff‐Äquilibrierung in cyclischen C₆H‐Kationen in der Gasphase und zum Mechanismus der unimolekularen Ethylen‐Abspaltung