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21.3: Formation of hydrates, hemiacetals, acetals

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    225898
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    Addition of alcohols to form hemiacetals and acetals

    In this organic chemistry topic, we shall see how alcohols (R-OH) add to carbonyl groups. Carbonyl groups are characterized by a carbon-oxygen double bond. The two main functional groups that consist of this carbon-oxygen double bond are Aldehydes and Ketones.

    Introduction

    It has been demonstrated that water adds rapidly to the carbonyl function of aldehydes and ketones to form geminal-diol. In a similar reaction alcohols add reversibly to aldehydes and ketones to form hemiacetals (hemi, Greek, half). This reaction can continue by adding another alcohol to form an acetal. Hemiacetals and acetals are important functional groups because they appear in sugars.

    To achieve effective hemiacetal or acetal formation, two additional features must be implemented. First, an acid catalyst must be used because alcohol is a weak nucleophile; and second, the water produced with the acetal must be removed from the reaction by a process such as a molecular sieves or a Dean-Stark trap. The latter is important, since acetal formation is reversible. Indeed, once pure hemiacetal or acetals are obtained they may be hydrolyzed back to their starting components by treatment with aqueous acid and an excess of water.

    Formation of hemiacetals

    OrganicCore_AldehydesKetones38.png

    Example 1: Formation of Hemiacetals

    OrganicCore_AldehydesKetones39.png

    Example 2: Hemiacetal Reversibility

     OrganicCore_AldehydesKetones40.png

    Formation of acetals

    Acetals are geminal-diether derivatives of aldehydes or ketones, formed by reaction with two equivalents (or an excess amount) of an alcohol and elimination of water. Ketone derivatives of this kind were once called ketals, but modern usage has dropped that term. It is important to note that a hemiacetal is formed as an intermediate during the formation of an acetal.

    OrganicCore_AldehydesKetones41.png

    Example 3: Formation of Acetals

    OrganicCore_AldehydesKetones42.png

    Examples

    Example 4: Acetal Reversibility

    OrganicCore_AldehydesKetones43.png

    Mechanism for hemiacetal and acetal formation

    The mechanism shown here applies to both acetal and hemiacetal formation

    1) Protonation of the carbonyl

    OrganicCore_AldehydesKetones44.png

    2) Nucleophilic attack by the alcohol

    OrganicCore_AldehydesKetones45.png

    3) Deprotonation to form a hemiacetal

    OrganicCore_AldehydesKetones46.png

    4) Protonation of the alcohol

    OrganicCore_AldehydesKetones47.png

    5)  Removal of water

    OrganicCore_AldehydesKetones48.png

    6) Nucleophilic attack by the alcohol

    OrganicCore_AldehydesKetones49.png

    7) Deprotonation by water

    OrganicCore_AldehydesKetones50.png

    Formation of cyclic hemiacetals and acetals

    Molecules which have an alcohol and a carbonyl can undergo an intramolecular reaction to form a cyclic hemiacetal.

    OrganicCore_AldehydesKetones51.png

    Intramolecular Hemiacetal formation is common in sugar chemistry. For example, the common sugar glucose exists in the cylcic manner more than 99% of the time in a mixture of aqueous solution.

    OrganicCore_AldehydesKetones52.png

    Carbonyls reacting with diol produce a cyclic acetal.  A common diol used to form cyclic acetals is ethylene glycol.

    OrganicCore_AldehydesKetones53.png

    Acetals as protecting groups

    The importance of acetals as carbonyl derivatives lies chiefly in their stability and lack of reactivity in neutral to strongly basic environments. As long as they are not treated by acids, especially aqueous acid, acetals exhibit all the lack of reactivity associated with ethers in general. Among the most useful and characteristic reactions of aldehydes and ketones is their reactivity toward strongly nucleophilic (and basic) metallo-hydride, alkyl and aryl reagents. If the carbonyl functional group is converted to an acetal these powerful reagents have no effect; thus, acetals are excellent protective groups, when these irreversible addition reactions must be prevented.

    In the following example we would like a Grignard reagent to react with the ester and not the ketone.  This cannot be done without a protecting group because Grignard reagents react with esters and ketones.

    OrganicCore_AldehydesKetones54.png

    References

    1. Vollhardt, K. Peter C., and Neil E. Schore. Organic Chemistry: Structure and Function. New York: W.H. Freeman and Company, 2007
    2. Carey, Francis. Advanced Organic Chemistry. 5th ed. Springer, 2007.

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