Alkane and Cycloalkane Transformations in Superelectrophilic Liquids

Akhrem, I. S.; Orlinkov, A. V.; Vol'pin, M. E.

doi:10.1007/978-94-010-0127-4_28

Cited by 2 publications

(1 citation statement)

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“…As relatively weak electrophiles, acyl cations do not react with saturated hydrocarbons. Olah has suggested that the de facto reactive intermediates in the reaction of acyl ions with hydrocarbons under superacidic conditions are not the acyl cations themselves but their O-protonated (protosolvated) forms R−COH 2+ ( 7 ), which in the extreme case are highly electron-deficient superelectrophilic gitonic dications substantially more reactive than their parent monocations due to substantially decreased neighboring oxygen stabilization . Similarly, Vol'pin et al found that 2 or more equiv of anhydrous aluminum chloride brings about readily superelectrophilic reaction of acyl cations.…”

Section: Resultsmentioning

confidence: 99%

Acid-Catalyzed Isomerization of Pivalaldehyde to Methyl Isopropyl Ketone via a Reactive Protosolvated Carboxonium Ion Intermediate

et al. 2001

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Quantitative rearrangement of pivalaldehyde to methyl isopropyl ketone is observed in acids such as trifluoromethanesulfonic acid, anhydrous HF, and trifluoroethyl alcohol-BF3 but not in trifluoroacetic acid. Studies in a mixture of trifluoroacetic acid and trifluoromethanesulfonic acid show that acids with H(o) < or = -11 are able to carry out complete isomerization. These results and density functional theory calculations at the B3LYP/6-31G level suggest that protonated pivalaldehyde undergoes further protosolvation at higher acidities to a reactive superelectrophilic species resulting in rearrangement. A mechanism for the pivalaldehyde rearrangement to methyl isopropyl ketone in strong protic acids involving a reactive protosolvated superelectrophilic intermediate is suggested. Aspects of the related mechanism of the reaction with isobutane with CO in HF/BF3 medium leading to methyl isopropyl ketone are also discussed.

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Section: Resultsmentioning

confidence: 99%