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Query: UMLS:C0344329 (
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28,634
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Low-temperature ozonation (-78 degrees 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.
...
PMID:Evidence for the HOOO(-) anion in the ozonation of 1,3-dioxolanes: hemiortho esters as the primary products. 1223 27