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    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

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    Meldrum's acid is exceptionally acidic compared to similar acyclic compounds due to its cyclic structure. Its acidity decreases as the ring size increases, with larger ring compounds having similar acidity to dimethyl malonate. The enhanced acidity of Meldrum's acid is due to stabilization of the conjugate base by the cyclic structure.

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    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

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    Meldrum's acid is exceptionally acidic compared to similar acyclic compounds due to its cyclic structure. Its acidity decreases as the ring size increases, with larger ring compounds having similar acidity to dimethyl malonate. The enhanced acidity of Meldrum's acid is due to stabilization of the conjugate base by the cyclic structure.

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    Meldrum's acid is exceptionally acidic compared to similar acyclic compounds due to its cyclic structure. Its acidity decreases as the ring size increases, with larger ring compounds having similar acidity to dimethyl malonate. The enhanced acidity of Meldrum's acid is due to stabilization of the conjugate base by the cyclic structure.

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    29 views1 page

    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

    Uploaded by

    panda biru
    Meldrum's acid is exceptionally acidic compared to similar acyclic compounds due to its cyclic structure. Its acidity decreases as the ring size increases, with larger ring compounds having similar acidity to dimethyl malonate. The enhanced acidity of Meldrum's acid is due to stabilization of the conjugate base by the cyclic structure.

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    of 1

    6.10.

    Meldrum’s acid, pK = 73, is exceptionally acidic in comparison with 623


    acyclic analogs, such as dimethyl malonate (pK = 159). 5,5-Dimethyl-
    PROBLEMS
    1,3-cyclohexadione is only moderately more acidic than pentane-2,4-dione.
    (pK = 112 versus 13.43). (All pK values in DMSO). It is found that the enhanced
    acidity of Meldrum’s acid derivatives decreases as the ring size increases, with
    the larger ring compounds being similar in acidity to dimethyl malonate. Analyze
    the factors that contribute to the enhanced acidity of Meldrum’s acid.
    O O
    O O pK
    O O
    CH3O2CCH2CO2CH3 O O n=5 13.0
    (CH2)n
    CH3 CH3 n=8 15.2
    pK = 15.9 15.1
    n = 12
    pK = 7.3

    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.

    a. The enol content of the 2-isomer of 3-(x-pyridyl)-3-oxopropanoate esters is


    higher than for the 3- and 4-isomers.
    position Kenol
    CCH2CO2C2H5 2 0.86
    N 3 0.15
    O
    4 0.19

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