Return Equilibrium Characterized by K: O O CH O CCH CO CH O O (CH) N O O PK 13.0 15.2 15.1 O
Return Equilibrium Characterized by K: O O CH O CCH CO CH O O (CH) N O O PK 13.0 15.2 15.1 O
Return Equilibrium Characterized by K: O O CH O CCH CO CH O O (CH) N O O PK 13.0 15.2 15.1 O
6.11. In some solvents, such as K + ·− OR-DMSO, it can be shown that the internal
return equilibrium characterized by k1 /k−1 is fast relative to the dissociation
process characterized by k2 . In this process, the base returns the proton to the
carbanion faster than the proton donor exchanges with other molecules from
solution. If internal return is important under a given set of conditions, how
might that affect the correlation between observed kinetic and thermodynamic
acidity? How can the occurrence of internal return be detected experimentally?
k1 k2
R3C H + B R3C– H B R3C– + H S
k-1
6.12. Discuss the following comparison of the enol content at equilibrium based on
data given in Table 6.12. Discuss the reason for the differing enol content of the
pairs of compounds in question.
a. Why does cyclohexanone have a somewhat higher enol content than cyclopen-
tanone?
b. Why do methyl acetate and acetamide have much lower enol content than
acetone?
c. Why does 2-indanone have a much higher enol content than 1-indanone?
d. Why does 5,5-dimethyl-1,3-cyclohexa-1,3-dione have a higher enol content
than acyclic diones such as acetylacetone, even though intramolecular
hydrogen bonding is not possible?
6.13. Identify the structural factors that lead to the special stabilization of the enol
form noted in each example.