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    Aldehydes and Ketones: Nucleophilic Addition Reactions

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    Sandipan Saha

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    Aldehydes and Ketones: Nucleophilic Addition Reactions

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    Aldehydes and Ketones: Nucleophilic Addition Reactions

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    Sandipan Saha

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    © All Rights Reserved
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    20 Aldehydes and Ketones:

    Nucleophilic Addition
    Reactions

    Davanone

    In the preceding chapter, we saw that the chemistry of the carbonyl group depends upon its polarity.
    In this chapter, we will examine the differences in stability and reactivity of aldehydes and ketones.
    Many of the reactions we will discuss occur by addition of a nucleophile to the carbonyl carbon and
    the addition of an electrophile to the carbonyl oxygen. Sometimes, these reactions produce a stable,
    tetrahedral adduct. In other cases, the tetrahedral adduct undergoes further reaction. Nucleophilic
    addition to carbonyl groups is a major new class of reaction mechanism.

    20.1 Ketones are more stable than aldehydes. If a reactant is stable, a reaction that destroys its structure is
    RELATIVE STABILITIES less likely to take place. The carbonyl group of either an aldehyde or a ketone has two resonance forms.
    OF ALDEHYDES AND In one form, the carbonyl carbon has a positive charge and the carbonyl oxygen atom has a negative
    charge. We know that alkyl groups stabilize carbocations. Thus, the dipolar resonance form of pro-
    KETONES panone, in which the carbonyl carbon is bonded to two alkyl groups, is more stable than the dipolar
    resonance form of propanal, which is bonded to one alkyl group and a hydrogen atom. The dipolar
    resonance form of a ketone is a secondary oxycarbocation; the dipolar resonance form of an aldehyde
    is a primary oxycarbocation. The secondary oxycarbocation is more stable. Thus, the carbonyl carbon
    of aldehydes is more electrophilic than the carbonyl carbon of ketones.

    O O

    CH3 C CH3 CH3 C CH3

    propanone dipolar resonance structure,


    secondary oxycarbocation

    O O

    CH3 CH2 C H CH3 CH2 C H

    propanal dipolar resonance structure,


    primary oxycarbocation
    The importance of the dipolar resonance forms is reflected in the stabilities of isomeric carbonyl com-
    pounds. Propanal is approximately 27 kJ mole-1 less stable than propanone. For addition reactions, two
    isomeric products with different stabilities also form. Therefore, we also have to consider the relative
    stabilities of the products. Hydrogenation of propanal and propanone gives isomeric alcohols. 1-Propa-
    nol is approximately 16 kJ mole-1 less stable than 2-propanol. Because the differences in the stabilities
    of the reactants is greater than the difference in the stabilities of the products, the equilibrium constants
    for the addition reactions of carbonyl compounds depend more on differences in the structure of the
    carbonyl compound than on the differences in the structure of the addition product. Thus, because ke-
    tones are more stable than aldehydes, the addition reactions of ketones are less favorable (have smaller
    equilibrium constants) than addition reactions of aldehydes.

    Organic Chemistry. https://doi.org/10.1016/B978-0-12-812838-1.50020-7 Copyright © 2018 Elsevier Inc. All rights reserved. 595

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