Gas-phase chemistry of acylium ions: Seven-to-five ring contraction of 1,3-dioxepane and 1,3-dioxep-5-ene

Luiz Alberto B. Moraes, Tapio Kotiaho, Marcos N. Eberlin (Corresponding Author)

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Abstract

As shown by pentaquadrupole triple‐stage mass spectrometric and 18O‐labeling experiments, two seven‐membered cyclic acetals, 1,3‐dioxepane and 1,3‐dioxep‐5‐ene, fail to react by transacetalization with the gaseous acylium ions CH3C+=O and (CH3)2NC+=O. Instead, a novel and less exothermic but more kinetically favored reaction, seven‐to‐five ring contraction, occurs predominantly, and to great extents with the most reactive acylium ion, (CH3)2NC+=O. 1,3‐Dioxepane yields O‐acylated tetrahydrofurans; 1,3‐dioxep‐5‐ene yields O‐acylated 2,5‐dihydrofurans.
Original languageEnglish
Pages (from-to)670-676
JournalJournal of Mass Spectrometry
Volume34
Issue number6
DOIs
Publication statusPublished - 1999
MoE publication typeA1 Journal article-refereed

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Moraes, Luiz Alberto B. ; Kotiaho, Tapio ; Eberlin, Marcos N. / Gas-phase chemistry of acylium ions : Seven-to-five ring contraction of 1,3-dioxepane and 1,3-dioxep-5-ene. In: Journal of Mass Spectrometry. 1999 ; Vol. 34, No. 6. pp. 670-676.
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title = "Gas-phase chemistry of acylium ions: Seven-to-five ring contraction of 1,3-dioxepane and 1,3-dioxep-5-ene",
abstract = "As shown by pentaquadrupole triple‐stage mass spectrometric and 18O‐labeling experiments, two seven‐membered cyclic acetals, 1,3‐dioxepane and 1,3‐dioxep‐5‐ene, fail to react by transacetalization with the gaseous acylium ions CH3C+=O and (CH3)2NC+=O. Instead, a novel and less exothermic but more kinetically favored reaction, seven‐to‐five ring contraction, occurs predominantly, and to great extents with the most reactive acylium ion, (CH3)2NC+=O. 1,3‐Dioxepane yields O‐acylated tetrahydrofurans; 1,3‐dioxep‐5‐ene yields O‐acylated 2,5‐dihydrofurans.",
author = "Moraes, {Luiz Alberto B.} and Tapio Kotiaho and Eberlin, {Marcos N.}",
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Gas-phase chemistry of acylium ions : Seven-to-five ring contraction of 1,3-dioxepane and 1,3-dioxep-5-ene. / Moraes, Luiz Alberto B.; Kotiaho, Tapio; Eberlin, Marcos N. (Corresponding Author).

In: Journal of Mass Spectrometry, Vol. 34, No. 6, 1999, p. 670-676.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Gas-phase chemistry of acylium ions

T2 - Seven-to-five ring contraction of 1,3-dioxepane and 1,3-dioxep-5-ene

AU - Moraes, Luiz Alberto B.

AU - Kotiaho, Tapio

AU - Eberlin, Marcos N.

N1 - Project code: K9SU00137

PY - 1999

Y1 - 1999

N2 - As shown by pentaquadrupole triple‐stage mass spectrometric and 18O‐labeling experiments, two seven‐membered cyclic acetals, 1,3‐dioxepane and 1,3‐dioxep‐5‐ene, fail to react by transacetalization with the gaseous acylium ions CH3C+=O and (CH3)2NC+=O. Instead, a novel and less exothermic but more kinetically favored reaction, seven‐to‐five ring contraction, occurs predominantly, and to great extents with the most reactive acylium ion, (CH3)2NC+=O. 1,3‐Dioxepane yields O‐acylated tetrahydrofurans; 1,3‐dioxep‐5‐ene yields O‐acylated 2,5‐dihydrofurans.

AB - As shown by pentaquadrupole triple‐stage mass spectrometric and 18O‐labeling experiments, two seven‐membered cyclic acetals, 1,3‐dioxepane and 1,3‐dioxep‐5‐ene, fail to react by transacetalization with the gaseous acylium ions CH3C+=O and (CH3)2NC+=O. Instead, a novel and less exothermic but more kinetically favored reaction, seven‐to‐five ring contraction, occurs predominantly, and to great extents with the most reactive acylium ion, (CH3)2NC+=O. 1,3‐Dioxepane yields O‐acylated tetrahydrofurans; 1,3‐dioxep‐5‐ene yields O‐acylated 2,5‐dihydrofurans.

U2 - 10.1002/(SICI)1096-9888(199906)34:6<670::AID-JMS819>3.0.CO;2-H

DO - 10.1002/(SICI)1096-9888(199906)34:6<670::AID-JMS819>3.0.CO;2-H

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