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    Carbonyl compounds-II S-1

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    sciencewing rbi
    The document discusses reactions involving carbonyl compounds, specifically the acidity of α-hydrogens and mechanisms of aldol condensation, Perkin's condensation, and Claisen's condensation. The α-hydrogens of carbonyl compounds are unusually acidic due to stabilization of the resulting enolate ion through resonance structures that delocalize the negative charge. Aldol condensation involves addition of enolates to carbonyl groups, forming β-hydroxy compounds that can undergo dehydration to α,β-unsaturated carbonyl products. Perkin's condensation produces α,β-unsaturated acids from aromatic aldehydes and acid anhydrides. Claisen's condensation synthesizes β-keto

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    Carbonyl compounds-II S-1

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    sciencewing rbi
    49 views5 pages
    The document discusses reactions involving carbonyl compounds, specifically the acidity of α-hydrogens and mechanisms of aldol condensation, Perkin's condensation, and Claisen's condensation. The α-hydrogens of carbonyl compounds are unusually acidic due to stabilization of the resulting enolate ion through resonance structures that delocalize the negative charge. Aldol condensation involves addition of enolates to carbonyl groups, forming β-hydroxy compounds that can undergo dehydration to α,β-unsaturated carbonyl products. Perkin's condensation produces α,β-unsaturated acids from aromatic aldehydes and acid anhydrides. Claisen's condensation synthesizes β-keto

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    The document discusses reactions involving carbonyl compounds, specifically the acidity of α-hydrogens and mechanisms of aldol condensation, Perkin's condensation, and Claisen's condensation. The α-hydrogens of carbonyl compounds are unusually acidic due to stabilization of the resulting enolate ion through resonance structures that delocalize the negative charge. Aldol condensation involves addition of enolates to carbonyl groups, forming β-hydroxy compounds that can undergo dehydration to α,β-unsaturated carbonyl products. Perkin's condensation produces α,β-unsaturated acids from aromatic aldehydes and acid anhydrides. Claisen's condensation synthesizes β-keto

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    49 views5 pages

    Carbonyl compounds-II S-1

    Uploaded by

    sciencewing rbi
    The document discusses reactions involving carbonyl compounds, specifically the acidity of α-hydrogens and mechanisms of aldol condensation, Perkin's condensation, and Claisen's condensation. The α-hydrogens of carbonyl compounds are unusually acidic due to stabilization of the resulting enolate ion through resonance structures that delocalize the negative charge. Aldol condensation involves addition of enolates to carbonyl groups, forming β-hydroxy compounds that can undergo dehydration to α,β-unsaturated carbonyl products. Perkin's condensation produces α,β-unsaturated acids from aromatic aldehydes and acid anhydrides. Claisen's condensation synthesizes β-keto

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    of 5

    Chemistry IV sem Carbonyl compounds-II

    Session 1: Acidity of α-hydrogens, mechanism of aldol condensation,


    Perkin’s condensation, Claisen’s condensation

    In this chapter we shall discuss reactions that derive from the weak acidity of
    hydrogen atoms on carbon atoms adjacent to a carbonyl group. These hydrogen
    atoms are called the α-hydrogens, and the carbon to which they are attached is
    called the α-carbon.

    Acidity of α-hydrogens of carbonyl compounds: Enolate Anions


    When we say that the α-hydrogens of carbonyl compounds are acidic, we mean that
    they are unusually acidic for hydrogen atoms attached to carbon.

    • The pKa values for the α hydrogens of most simple aldehydes or ketones are of the
    order of 19–20.
    This means that they are more acidic than hydrogen atoms of ethyne, pKa=25, and are
    far more acidic than the hydrogens of ethene (pKa=44) or of ethane (pKa=50).
    The reasons for the unusual acidity of the α−hydrogens of carbonyl compounds are
    straightforward.

    • The carbonyl group is strongly electron withdrawing, and when a carbonyl compound
    loses an α-proton, the anion that is produced, called an enolate, is stabilized by
    delocalization.

    Two resonance structures, A and B, can be written for the enolate. In structure A the
    negative charge is on carbon, and in structure B the negative charge is on oxygen. Both
    structures contribute to the hybrid. Although structure A is favored by the strength of its
    carbon–oxygen p bond relative to the weaker carbon–carbon p bond of B, structure B
    makes a greater contribution to the hybrid because oxygen, being highly electronegative,

    1
    Digital Learning-DCE Karnatak University
    Chemistry IV sem Carbonyl compounds-II

    is better able to accommodate the negative charge. We can depict the enolate hybrid in the
    following way:

    When this resonance-stabilized enolate accepts a proton, it can do so in either of two ways:
    It can accept the proton at carbon to form the original carbonyl compound in what is called
    the keto form or it may accept the proton at oxygen to form an enol (alkene alcohol).

    • The enolate is the conjugate base of both the enol and keto forms.

    Aldol Reactions: Addition of Enolates and Enols to Aldehydes and


    Ketones
    • Aldol additions and aldol condensations together represent an important class of
    carbon–carbon bond-forming reaction.
    An aldol reaction begins with addition of an enolate or enol to the carbonyl group of
    an aldehyde or ketone, leading to a β-hydroxy aldehyde or ketone as the initial product. A
    simple
    example is shown below, whereby two molecules of acetaldehyde (ethanal) react to form
    3-hydroxybutanal. 3-Hydroxybutanal is an “aldol” because it contains both an aldehyde and
    an alcohol functional group. Reactions of this general type are known as aldol additions.

    Aldol Addition Reactions

    An aldol addition is an equilibrium reaction when it is conducted in a protic solvent with


    a base such as hydroxide or an alkoxide. The mechanism for an aldol addition involving
    an aldehyde is shown below.

    2
    Digital Learning-DCE Karnatak University
    Chemistry IV sem Carbonyl compounds-II

    Aldol Condensation Reactions: Dehydration of Aldol Addition Product


    Dehydration of an aldol addition product leads to a conjugated α,β-unsaturated carbonyl
    system. The overall process is called an aldol condensation, and the product can be called
    an enal (alkene aldehyde) or enone (alkene ketone), depending on the carbonyl group in
    the product. The stability of the conjugated enal or enone system means that the dehydration equilibrium
    is essentially irreversible. For example, the aldol addition reaction that leads
    to 3-hydroxybutanal, dehydrates on heating to form 2-butenal. A
    mechanism for the dehydration is shown here.

    The Perkin condensation


    The Perkin condensation is an aldol-type condensation in which an aromatic aldehyde
    (ArCHO) reacts with a carboxylic acid anhydride, (RCH2CO)2O, to give an a,b-unsaturated acid
    (ArCH=CRCO2H). The catalyst that is usually employed is the potassium salt of the carboxylic
    acid (RCH2CO2K)
    Cinnamic acid synthesis from aryl aldehyde and acetic anhydride

    3
    Digital Learning-DCE Karnatak University
    Chemistry IV sem Carbonyl compounds-II

    Mechanism:

    The Claisen Condensation: A Synthesis of β-Keto Esters


    The Claisen condensation is a carbon–carbon bond-forming reaction that is useful for
    synthesizing β-keto esters. In a Claisen condensation, the enolate of one ester molecule adds
    to the carbonyl group of another, resulting in an acyl substitution reaction that forms a β-keto
    ester and an alcohol molecule. The alcohol molecule that is formed derives from the alkoxyl
    group of the ester. A classic example is the Claisen condensation by which ethyl acetoacetate
    (acetoacetic ester) can be synthesized.

    4
    Digital Learning-DCE Karnatak University
    Chemistry IV sem Carbonyl compounds-II

    Mechanism:

    5
    Digital Learning-DCE Karnatak University

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