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19.5 Nucleophilic Addition of Water: Hydration

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    90968
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    Objectives

    After completing this section, you should be able to

    1. write the step‑wise mechanism for the base‑catalyzed hydration of an aldehyde or ketone.
    2. write the step‑wise mechanism for the acid‑catalyzed hydration of an aldehyde or ketone.
    Key Terms

    Make certain that you can define, and use in context, the key term below.

    • geminal (gem) diol

    It has been demonstrated that water, in the presence of an acid or a base, adds rapidly to the carbonyl function of aldehydes and ketones establishing a reversible equilibrium with a hydrate (geminal-diol or gem-diol). The word germinal or gem comes from the Latin word for twin, geminus.

    Example 19.5.1

    Going from Reactants to Products Simplified

    Reaction diagram. Carbonyl has the carbon-oxygen double bond change to a single bond. A hydroxyl group is added to the carbon and a hydrogen is added to the oxygen.

    Reversibility of the ReactionEdit section

    Isolation of gem-diols is difficult because the reaction is reversibly. Removal of the water during a reaction can cause the conversion of a gem-diol back to the corresponding carbonyl.


    Factors Affecting the Gem-diol EquilibriumEdit section

    In most cases the resulting gem-diol is unstable relative to the reactants and cannot be isolated. Exceptions to this rule exist, one being formaldehyde where the weaker pi-component of the carbonyl double bond, relative to other aldehydes or ketones, and the small size of the hydrogen substituents favor addition. Thus, a solution of formaldehyde in water (formalin) is almost exclusively the hydrate, or polymers of the hydrate. The addition of electron donating alkyl groups stabilized the partial positive charge on the carbonyl carbon and decreases the amount of gem-diol product at equilibrium. Because of this ketones tend to form less than 1% of the hydrate at equilibrium. Likewise, the addition of strong electron-withdrawing groups destabilizes the carbonyl and tends to form stable gem-diols. Two examples of this are chloral, and 1,2,3-indantrione. It should be noted that chloral hydrate is a sedative and has been added to alcoholic beverages to make a “Knock-out” drink also called a Mickey Finn. Also, ninhydrin is commonly used by forensic investigators to resolve finger prints.

    Mechanism of Gem-diol Formation

    Edit section

    The mechanism is catalyzed by the addition of an acid or base. Note! This may speed up the reaction but is has not effect on the equilibriums discussed above. Basic conditions speed up the reaction because hydroxide is a better nucleophilic than water. Acidic conditions speed up the reaction because the protonated carbonyl is more electrophilic.

    Basic conditions

    1) Nucleophilic attack by hydroxide

    2) Protonation of the alkoxide


    Acidic conditions

    1) Protonation of the carbonyl

    2) Nucleophilic attack by water

    3) Deprotonation

    Exercises

    Exercise 19.5.1

    Draw the expected products of the following reactions.

    problem 1 structures.svg

    Answer

    answer 1 structures.svg

    Exercise 19.5.2

    Of the following pairs of molecules which would you expect to form a larger percentage of gem-diol at equilibrium? Please explain your answer.

    problem 2 structures.svg

    Answer

    The compound on the left would. Fluorine is more electronegative than bromine and would remove more electron density from the carbonyl carbon. This would destabilize the carbonyl allowing for more gem-diol to form.

    Exercise 19.5.3

    Would you expect the following molecule to form appreciable amount of gem-diol in water? Please explain your answer.

    problem 3 structure.svg

    Answer

    Although ketones tend to not form gem-diols, this compound exists almost entirely in the gem-diol form when placed in water. Ketones tend to not form gem-diols because of the stabilizing effect of the electron donating alkyl group. However, in this case the electron donating effects of the alkyl group is dominated by the presence of six highly electronegative fluorines turning these into electron withdrawing groups.

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    19.5 Nucleophilic Addition of Water: Hydration is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

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