Derivatives of Allylic Chlorides

Hearne, G.; Tamele, M.; Converse, W.

doi:10.1021/ie50378a028

Cited by 19 publications

(5 citation statements)

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“…7 Pinacol rearrangement (initiated by protonation of a double bond) has previously been observed for two isomers of MBO, 2-methyl-2-buten-1-ol and 3-methyl-3-buten-2-ol in 13% sulfuric acid, leading to a mixture of 3-methyl-2-butanone and 2-methyl-1-butanal. 37,38 Because this reaction has been observed to occur in weak acids, we believe that pinacol rearrangement is also responsible for the uptake we observed in 40 and 55 wt % H 2 SO 4 solutions. A mechanism similar to the one proposed in the previous studies is shown in Figure 7 for MBO.…”

Section: Discussionmentioning

confidence: 73%

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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Section: Discussionmentioning

confidence: 73%

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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“…If a 12% acid is used for this, practically quantitative yields can be obtained and the aldehyde is produced in very pure form [26]. The procedure can be made continuous if the methallyl alcohol is added to the sulphuric acid in the same amounts as the azeotropic mixture of aldehyde and water distilhng off.…”

Section: A) Hydrolysis Of Methallyl Chloride To Methallyl Alcohol Andmentioning

confidence: 99%

“…The oxidation of methallyl alcohol to methacrolein [29]. A dehydrogenation of methallyl alcohol to methacrolein over one of the usual dehydrogenation catalysts for alcohols does not give satisfactory results, since the addition of the methallyl alcohol to the isobutyraldehyde produced takes place.…”

Section: The Manufacture Of Isobutene Glycol (2-methylpropane-l2-diol)mentioning

confidence: 99%

The Chlorination of the Olefins

Asinger¹

1968

Mono-Olefins

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“…Although several patents (S, 4, 18, 32) have been issued covering the oxidation of methallyl alcohol to methacrolein, as well as the oxidation of methacrolein to methacrylic acid, little is disclosed in the literature relative to these oxidations. Some general information is found concerning the oxidation of methallyl alcohol with chemical oxidizing agents such as potassium persulfate or silver oxide, but there is little information concerning the use of air or oxygen for the oxidation (12). Some mention is made of the corresponding allyl compounds, and their similarity to the methallyl derivatives in their physical properties and chemical reactions was to some extent useful in this investigation (5, 6, 35).…”

Section: Oxidation Of Methallyl Alcoholmentioning

confidence: 99%

“…In the paper by Hearne (12) the use of a silver or copper catalyst is suggested in the oxidation of methallyl alcohol with oxygen using temperatures of 500°to 550°C. This range of temperature is considerably higher than that employed by Zimakov and Pokrovskii for allyl alcohol.…”

Section: Oxidation Of Methallyl Alcoholmentioning

confidence: 99%