71302-96-0Relevant articles and documents
13C magnetic resonance studies. 142. The fate of highly substituted acyclic ketones in strong base: β-enolization, Haller-Bauer cleavage, and an alkyl to aryl acyl shift
Dyllick-Brenzinger, Rainer A.,Patel, Vijay,Rampersad, Mollin B.,Stothers, J. B.,Thomas, Shirley E.
, p. 1106 - 1115 (2011/08/10)
Di-tert-butyl ketone (2a), 5,5,7,7-tetramethyl-6-undecanone (2b), and 2,4-dimethyl-2,4-diphenyl-3-pentanone (2d) have been found to undergo slow rearrangement by β-proton abstraction from the α-methyl groups upon treatment with t-BuO-/t-BuOH/>185 deg C.This is in contrast to the absence of such rearrangement in cyclic systems.It is the only significant process observed for 2a and 2b, whereas with 2d and its monomethyl analog 22 Haller-Bauer type cleavage and an unprecedented 1,3-acyl shift from sp3 to sp2 carbon accompany the β-enolate rearrangement.The rates of 1H/2H exchange of the methyl protons in 2a, b were found to be similar to those reported for a variety of cyclic systems but this exchange does not occur in 2d, where only aryl proton exchange was observed.
