Evidence for the HOOO- anion in the ozonation of 1,3-dioxolanes: hemiortho esters as the primary products

Božo Plesničar, Janez Cerkovnik, Tell Tuttle, Elfi Kraka, Dieter Cremer

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

Low-temperature ozonation (-78 °C) of 2-methyl-1,3-dioxolane (1a) in acetone-d6, methyl acetate, and tert-butyl methyl ether produced both the corresponding acetal hydrotrioxide (3a, ROOOH) and the hemiortho ester (2a, ROH) in molar ratio 1:5. Both intermediates were fully characterized by 1H, 13C, and 17O NMR spectroscopy, and they both decomposed to the corresponding hydroxy ester at higher temperatures. The mechanism involving the HOOO- anion formed by the abstraction of the hydride ion by ozone to form an ion pair, R+ -OOOH, with its subsequent collapse to either the corresponding hemiortho ester (ROH) or the acetal hydrotrioxide (ROOOH) was proposed. This mechanism is supported by the PISA/B3LYP/6-311++G(3df,3pd) calculations.

LanguageEnglish
Pages11260-11261
Number of pages2
JournalJournal of the American Chemical Society
Volume124
Issue number38
Early online date28 Aug 2002
DOIs
Publication statusPublished - 25 Sep 2002

Fingerprint

Ozonization
Anions
Acetals
Esters
Negative ions
Ions
Temperature
Ozone
Acetone
Hydrides
Nuclear magnetic resonance spectroscopy
Ethers
Magnetic Resonance Spectroscopy
formal glycol

Keywords

  • low-temperature ozonation
  • decomposition
  • organic materials

Cite this

Plesničar, Božo ; Cerkovnik, Janez ; Tuttle, Tell ; Kraka, Elfi ; Cremer, Dieter. / Evidence for the HOOO- anion in the ozonation of 1,3-dioxolanes : hemiortho esters as the primary products. In: Journal of the American Chemical Society . 2002 ; Vol. 124, No. 38. pp. 11260-11261.
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Evidence for the HOOO- anion in the ozonation of 1,3-dioxolanes : hemiortho esters as the primary products. / Plesničar, Božo; Cerkovnik, Janez; Tuttle, Tell; Kraka, Elfi; Cremer, Dieter.

In: Journal of the American Chemical Society , Vol. 124, No. 38, 25.09.2002, p. 11260-11261.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Evidence for the HOOO- anion in the ozonation of 1,3-dioxolanes

T2 - Journal of the American Chemical Society

AU - Plesničar, Božo

AU - Cerkovnik, Janez

AU - Tuttle, Tell

AU - Kraka, Elfi

AU - Cremer, Dieter

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AB - Low-temperature ozonation (-78 °C) of 2-methyl-1,3-dioxolane (1a) in acetone-d6, methyl acetate, and tert-butyl methyl ether produced both the corresponding acetal hydrotrioxide (3a, ROOOH) and the hemiortho ester (2a, ROH) in molar ratio 1:5. Both intermediates were fully characterized by 1H, 13C, and 17O NMR spectroscopy, and they both decomposed to the corresponding hydroxy ester at higher temperatures. The mechanism involving the HOOO- anion formed by the abstraction of the hydride ion by ozone to form an ion pair, R+ -OOOH, with its subsequent collapse to either the corresponding hemiortho ester (ROH) or the acetal hydrotrioxide (ROOOH) was proposed. This mechanism is supported by the PISA/B3LYP/6-311++G(3df,3pd) calculations.

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