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    Lecture Notes Chemistry 342-2008 Mukund P. Sibi: Alpha

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    Ayesha
    1) The alpha-carbon of carbonyl compounds (aldehydes, ketones, acids, and derivatives) has modest acidity and its C-H bond can be deprotonated to form a carbon nucleophile. 2) Carbonyl compounds exist in equilibrium with their enol isomers, though the keto form is generally favored. 3) Both acids and bases can catalyze the keto-enol tautomerism through protonation/deprotonation of the carbonyl oxygen or alpha carbon respectively.

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    Lecture Notes Chemistry 342-2008 Mukund P. Sibi: Alpha

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    Ayesha
    33 views3 pages
    1) The alpha-carbon of carbonyl compounds (aldehydes, ketones, acids, and derivatives) has modest acidity and its C-H bond can be deprotonated to form a carbon nucleophile. 2) Carbonyl compounds exist in equilibrium with their enol isomers, though the keto form is generally favored. 3) Both acids and bases can catalyze the keto-enol tautomerism through protonation/deprotonation of the carbonyl oxygen or alpha carbon respectively.

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    Tautomerism

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    1) The alpha-carbon of carbonyl compounds (aldehydes, ketones, acids, and derivatives) has modest acidity and its C-H bond can be deprotonated to form a carbon nucleophile. 2) Carbonyl compounds exist in equilibrium with their enol isomers, though the keto form is generally favored. 3) Both acids and bases can catalyze the keto-enol tautomerism through protonation/deprotonation of the carbonyl oxygen or alpha carbon respectively.

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    33 views3 pages

    Lecture Notes Chemistry 342-2008 Mukund P. Sibi: Alpha

    Uploaded by

    Ayesha
    1) The alpha-carbon of carbonyl compounds (aldehydes, ketones, acids, and derivatives) has modest acidity and its C-H bond can be deprotonated to form a carbon nucleophile. 2) Carbonyl compounds exist in equilibrium with their enol isomers, though the keto form is generally favored. 3) Both acids and bases can catalyze the keto-enol tautomerism through protonation/deprotonation of the carbonyl oxygen or alpha carbon respectively.

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    Lecture Notes Chemistry 342-2008 Mukund P.

    Sibi
    Lecture 29
    Reactions at the Alpha-Carbon of Carbonyl Compounds
    "
    O H2
    C C Both the ! and !' hydrogens are acidic. However, the " and #
    H3C C CH3 hydrogens are not acidic.
    H2
    !' ! #

    The C-H bond on the alpha carbon of carbonyl compounds (aldehydes, ketones, acids,
    and acid derivatives) have modest acidity (pKa 17-25) depending on the functional group.
    The alpha C-H bond can be deprotonated to create a carbon nucleophile. The carbonyl
    compounds exit in an equilibrium with their enol isomers (alkene alcohols). The
    equilibrium is generally towards the carbonyl compound. The ketone and its enol
    counterpart are tautomers, compounds with different structures. They are not resonance
    structures.

    H
    O rapid O
    H C H H H
    C C C C
    H H H
    H H H H
    Ketone Enol
    C-H on H
    !-carbon O O
    H
    C rapid C
    H H

    aldehyde Hydrogen Enol

    Aldehydes and ketones with no C-H bonds on the !-carbon

    O O O
    O CH3
    C C C
    H H3C C
    C H
    H3C
    CH3

    In general, carbonyl compounds exist in their keto form. For example, at equilibrium, the
    enol tautomer of acetone is present in about 0.0000001%. In comparison to aldehydes
    and ketones, carboxylic acids and its derivatives have even lower amounts of enol form.

    The keto-enol tautomerism of carbonyl compounds is catalyzed by both acids and bases.
    The mechanism for acid and base catalysis of keto-enol tautomerism is shown here. In
    the acid catalyzed process, protonation of the carbonyl oxygen allows provides the
    oxonium ion. The acidity of the alpha proton is increased by the positive charge on the
    carbonyl carbon. Deprotonation by the base (just like E2 elimination) provides the enol.
    Lecture Notes Chemistry 342-2008 Mukund P. Sibi
    Lecture 29

    H+ H H H
    O O O Base O
    C H C H C H C + BH+

    Ketone Enol

    The base catalyzed enoalization also provides an enol from a carbonyl compound. In this
    case the base deprotonates the alpha proton that is rendered acidic by the carbonyl group.
    Water than protonates the oxygen to provide the enol and the base catalyst.

    O
    H H H
    O OH O O O
    H
    C C C C + HO
    C C C

    Ketone Enol

    Alpha-Substitution Reactions: Reactivity of Enols:

    The enol tautomer of carbonyl compounds is nucleophilic on the α-carbon. Thus


    electrophiles will attack the alpha carbon.

    Aldehydes and ketones undergo halogenation on the α-carbon under acid catalysis. One
    can do chorination, bromination, and iodination. Mechanistic studies suggest that follows
    second order kinetics (substrate and acid catalyst) and the reaction rate is independent of
    halogen concentration. This means that halogenation occurs in a fast step which is after
    the rate determining step.

    O O
    C H C Br
    Br2
    C C
    H H H3CCO2H H H

    H H Base
    O O O O
    H Br Br C Br C Br
    C
    C H+ C
    C
    H
    C C
    H H H H H H H

    Further evidence for the mechanism comes from deuteration experiments. When one
    treats a ketone or an aldehyde with D3O+, all the C-H bonds are replaced by C-D.
    Lecture Notes Chemistry 342-2008 Mukund P. Sibi
    Lecture 29
    O O
    H D
    C
    C D3O+ C
    C
    H H D D

    The α-halo compounds are useful for preparing α,β-unsaturated carbonyl compounds.
    The halo compounds undergo dehydrohalogenation using a base.

    O O O

    Br2 Br Pyridine
    H+ heat

    Carboxylic acids do not form enols readily (the alpha C-H is not very acidic). However,
    they undergo halogenation with bromine and phosphorous tribromide. The reaction is
    called Hell-Volhard-Zelinski reaction.

    Br
    OH OH
    C 1. Br2, PBr3 C
    O 2. H2O O

    OH PBr3 Br Br Br2
    C C C
    O O OH

    Br Br
    Br OH
    C H2O C
    O O

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