Journal of the American Chemical Society p. 3640 - 3645 (1985)
Update date:2022-08-16
Topics:
Baigrie, Lynn M.
Cox, Robin A.
Slebocka-Tilk, Henryka
Tencer, Michal
Tidwell, Thomas T.
The condensation of acetaldehyde (1) to an equilibrium mixture of aldol (2) and crotonaldehyde (3) is second order in 1.An excess acidity analysis reveals that a water molecule is also involved in the rate-limiting step; the reaction is actually the base-assisted addition of vinyl alcohol to protonated 1, even in concentrated H2SO4.A previous report of a kinetically first-order conversion of 1 to 3 is shown to be due to the presence of a fast-reacting oligomer of 1.The reaction of 1 in D2SO4 leads to partially deuterated 3, a result ascribed to partial conversion of vinyl alcohol to deuterated 1.Hydrogen isotop exchange of 3 was also observed, but at a slower rate.The rates of enolization of 1 were studied by iodination and are consistent with previous results and the proposed mechanism.The interconversion of 2 and 3 is shown to proceed via the enol of 2; in this case the rate-limiting step is water attack on/water loss from protonated 3/2, not proton transfer at carbon.
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