A study of gaseous 3-membered ring oxonium and sulphonium ions

Levsen, K.; Heimbach, Heinz; Sande, C. C. Van De; Monstrey, J.

doi:10.1016/0040-4020(77)84060-x

Cited by 17 publications

(8 citation statements)

References 51 publications

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“…Intermediacy of open-chain transients in reaction [4b] appears unlikely on the following grounds. Extensive collisional activation analysis excludes that open-chain isomers of 7 may undergo significant cyclization even at relatively long ion lifetimes (17). This conclusion agrees with the absence of detectable yields of benzocyclic products from the acetaldehyde decay systems (Table 4), wherein only the open-chain 1-phenoxyethyl cations 13 are generated by attack of 1 on the 0 of the substrate.…”

Section: Discussionsupporting

confidence: 76%

Arylation of cyclic ethers by gaseous phenylium ions. Formation and behavior of phenoxenium ions in the gas phase

Fornarini¹,

Speranza²

1988

Can. J. Chem.

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SIMONETTA FORNARINI and MAUR~ZIO SPERANZA. Can. J. Chem. 66, 2506Chem. 66, (1988. Free, unsolvated phenylium ions formed by the spontaneous decay of 1,4-ditritiobenzene have been allowed to react with gaseous cyclic ethers (oxirane, propene oxide, and oxetane) and acetaldehyde in the pressure range 30-250 Torr and in the presence of a thermal radical scavenger (02, 4 Torr). The effects of a gaseous base (NMe3, 20 Ton) and of an energy moderator (He, 630-720 Torr) were also investigated. Phenylium ion confirms its considerable site selectivity, demonstrated by the distinct preference for the n-type center of the substrate, although appreciable insertion into the carbocyclic structure of propene oxide and oxetane is observed as well. The stability features of the ionic intermediates from addition of phenylium ion to selected substrates have been evaluated as well as their fragmentation and isomerization mechanisms. The behavior of gaseous phenylium ion toward cyclic ethers, in particular its ability to formally abstract an oxygen atom from the ether to give the phenoxenium ion, a reaction first observed in the present study, is discussed and compared with previous mechanistic investigations carried out in the gas phase and in solution. (He,. L'ion phCnylium confirme sa haute sClectivitC qui est dCmontrCe par sa prCfCrence marquCe pour le centre de type n du substrat m&me si on observe aussi une quantitC appreciable d'insertion dans la structure carbocyclique de l'oxyde de propene et de 1'oxCtanne. On a CvaluC les caracteristiques de stabilitC ainsi que les mCcanismes de fragmentation et dlisomCrisation des intermediaires ioniques obtenus par l'addition de l'ion phCnylium sur des substrats choisis. On discute du comportement de l'ion phCnylium gazeux vis-a-vis des Cthers cycliques, en particulier de sa facilitC d'arracher formellement un atome d'oxygene de 1'Cther pour donner l'ion phCnoxCnium, une reaction qui a CtC observee pour la premiere fois dans cette Ctude; on compare ce comportement avec celui observe dans des Ctudes mkcanistiques rapportCes antkrieurement et effectuees soit en phase gazeuse soit en solution.[Traduit par la revue]

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Section: Discussionsupporting

confidence: 76%

Arylation of cyclic ethers by gaseous phenylium ions. Formation and behavior of phenoxenium ions in the gas phase

Fornarini¹,

Speranza²

1988

Can. J. Chem.

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“…Analysis of the CA spectra showed that the major part of a was rearranged to CH 3 CH D S C CH 3 , as had also been observed for metastable a ions. 4,8 Labeling data (1a-f, Table 2 respectively. Also, a fraction of 1d retains the terminal CD 3 group (m/z 78).…”

Section: Loss Ofmentioning

confidence: 99%

“…The CA spectra of the two groups differ somewhat, especially in the abundances of the m/z 27, 45 and 60 ions. The ion at m/z 75 resulting from an˛-cleavage of 3 has been taken as the prototype for structure e. 3,8 This may be true insofar as 85% of 3 decompose by˛-cleavage, as can be seen from the spectrum of 3a. The CA spectrum of the ion at m/z 75 from 3, however, corresponds to those from 1c and 1d (a).…”

Section: Loss Ofmentioning

confidence: 99%

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Intermediacy of ion neutral complexes in the fragmentation of short-chain dialkyl sulfides

Filsak

Budzikiewicz

1999

J. Mass Spectrom.

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“…Mit Hilfe ausgefeilter Techniken, wie z.B. der Photoionisationsmassenspektrometrie (PIMS) [4], der Ionencyclotronresonanz (ICR) [5] oder der Stoßaktivierungsmassenspektrometrie (CA) [6] gelang es wohl, neben den Chloro-und Bromoderivaten von 1 (X = Cl, Br) auch andere cyclische Onium-Ionen nachzuweisen (X = SR [7]), OR [8], NR2 [9], SiMe3 [10]), der einwandfreie Nachweis für die Existenz stabiler Fluoronium-Ionen (X = F) konnte hingegen weder in kondensierter Phase noch in der Gasphase geführt werden. Dies ist insofern überraschend, als nach allen bisher durchgeführten quantenchemischen Berechnungen [11] Der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie danken wir für die Förderung dieser Arbeit.…”

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Zur intermediären Existenz von Ethylenfluoronium-Ionen in der Gasphase/ On the Intermediary Existence of Gaseous Ethylen Fluoronium Ions

Ciommer

Schwarz

1983

Zeitschrift Für Naturforschung B

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Abstract The long-sought ethylen fluoronium ion (2) is generated as an intermediate in the dissociative ionization of 1-fluoro-2-(p-methyl)phenoxy ethane (4). However, prior to collisionally induced dissociation 2 undergoes ring-opening, associated with hydrogen migration, to form 1-fluoroethyl cation (3). Other decomposition pathways of the molecular ions of 4 involve (i) direct formation of 3 via a combination of C-O-cleavage (loss of ArO -) and [1,2] hydrogen migration (18%) and (ii) complete positional loss of the a-and β-methylene hydrogen atoms (34%). The remaining 48% of the molecular ions of 4 dissociate via anchimeric assistance of the fluorine in the elimination of ArO·, thus giving rise to the formation of 2.

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A study of gaseous 3-membered ring oxonium and sulphonium ions

Cited by 17 publications

References 51 publications

Arylation of cyclic ethers by gaseous phenylium ions. Formation and behavior of phenoxenium ions in the gas phase

Arylation of cyclic ethers by gaseous phenylium ions. Formation and behavior of phenoxenium ions in the gas phase

Intermediacy of ion neutral complexes in the fragmentation of short-chain dialkyl sulfides

Zur intermediären Existenz von Ethylenfluoronium-Ionen in der Gasphase/ On the Intermediary Existence of Gaseous Ethylen Fluoronium Ions

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