The experimental detection of a retro-Prince reaction exemplified by a homogeneous acid-catalyzed decomposition of isopentenols

Ryabova, R. S.; Osipova, G. F.

doi:10.1007/bf00695839

Cited by 2 publications

(2 citation statements)

References 2 publications

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“…Isoprene can also be produced directly from carbocation 2. As a result, MBO321 in acidic media could convert into MBO232 (through the isomerization process) and yield isoprene (through the dehydration reaction), which is consistent with previous study (Ryabova and Osipova, 1994).…”

Section: Product Analysis From Mbo321 With H 2 Sosupporting

confidence: 88%

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

Liu

Wang

2015

Journal of Environmental Sciences

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Section: Product Analysis From Mbo321 With H 2 Sosupporting

confidence: 88%

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

Liu

Wang

2015

Journal of Environmental Sciences

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“…Dehydration is reversible, and water molecules can add to either ion, giving 2-methyl-3-butene-2-ol (MBO) or 3-methyl-2-butene-1-ol. The equilibrium between MBO, 3-methyl-2-butene-1-ol, and protonated isoprene has been observed in 25−50 wt % sulfuric acid solutions at 25 °C. − Both protonation and dehydration are reversible and can contribute to the effective H for MBO, but they are believed to be rapid and thus do not contribute to the observed irreversible uptake of MBO. 3-methyl-2-butene-1-ol is also likely to undergo pinacol rearrangement, which would potentially lead to 3-methylbutanal.…”

Section: Discussionmentioning

confidence: 99%

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

et al. 2006

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To investigate the link between molecular structure, reactivity, and partitioning of oxygenated organic compounds in acidic aerosols, the uptake of three compounds found in the atmosphere, methyl vinyl ketone (MVK), methacrolein (MACR), and 2-methyl-3-butene-2-ol (MBO), by sulfuric acid solutions has been measured using a rotated wetted-wall reactor (RWW) coupled to a chemical ionization mass spectrometer (CIMS). MVK was found to partition reversibly into 20-75 wt % H 2 SO 4 solutions, and we report Henry's law coefficients between 20 and 7000 M atm -1 over this range. A chemical reaction for MVK was likely responsible for the uptake observed for 80-96 wt % H 2 SO 4 solutions. We derive an upper limit to the aldol self-reaction rate coefficient for MVK in 80 wt % solution of ∼3 M -1 s -1 . MACR partitioned reversibly over most of the acidity range, and in contrast to that for MVK, the Henry's law coefficient was relatively independent of H 2 SO 4 content. These differences indicate that the increase of the coefficient with acidity is likely due to the ability of the carbonyl molecule to form an enol. These results indicate that aldol condensation can be facile in concentrated sulfuric acid solutions, but it should be negligibly slow in dilute acid solutions such as tropospheric aerosols. MBO uptake could be explained by a Henry's law coefficient that decreases slightly as acid content varies from 20 to 55 wt % H 2 SO 4 ; we also measured the value in water, 70 M atm -1 at 298 K. A steady-state uptake of MBO was observed onto 40-80 wt % H 2 SO 4 solutions, a reaction product was observed, and the reaction was tentatively identified as Pinacol rearrangement. Similar rearrangements could be at the origin of some substituted oxygenated species found in atmospheric aerosols.

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The experimental detection of a retro-Prince reaction exemplified by a homogeneous acid-catalyzed decomposition of isopentenols

Cited by 2 publications

References 2 publications

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

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