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24.4: Basicity of Arylamines

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    448821
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    As noted previously, arylamines are generally less basic than alkylamines. Anilinium ion has pKa = 4.63, for instance, whereas methylammonium ion has pKa = 10.64. Arylamines are less basic than alkylamines because the nitrogen lone-pair electrons are delocalized by interaction with the aromatic ring’s \(\pi\) electron system and are less available for bonding to H+. In resonance terms, arylamines are stabilized relative to alkylamines because of their five resonance forms.

    Five resonance forms of phenylamine. Migration of electrons in double bonds and nonbonding pairs to obtain structures is denoted by arrows.

    Much of the resonance stabilization is lost on protonation, however, so the energy difference between protonated and nonprotonated forms is higher for arylamines than it is for alkylamines. As a result, arylamines are less basic. Figure \(\PageIndex{1}\) illustrates this difference.

    The energy levels of four compounds, arylamine, alkylamine, aryl ammonium ion, and alkyl ammonium ion in increasing order. Aniline reacts with hydrogen ion to form anilinium ion.
    Figure \(\PageIndex{1}\): Arylamines have a larger positive ∆G° for protonation and are therefore less basic than alkylamines, primarily because of resonance stabilization of the ground state. Electrostatic potential maps show that lone-pair electron density is delocalized in the amine but the charge is localized in the corresponding ammonium ion.

    Substituted arylamines can be either more basic or less basic than aniline, depending on the substituent. Electron-donating substituents, such as –CH3, –NH2, and –OCH3, which increase the reactivity of an aromatic ring toward electrophilic substitution (Section 16.4), also increase the basicity of the corresponding arylamine. Electron-withdrawing substituents, such as –Cl, –NO2, and –CN, which decrease ring reactivity toward electrophilic substitution, also decrease arylamine basicity. Table \(\PageIndex{2}\) considers only p-substituted anilines, but similar trends are observed for ortho and meta derivatives.

    The reversible reaction of para-substituted amine with water to form para-substituted anilinium ion and hydroxide ion.

    Table \(\PageIndex{2}\) Base Strength of Some p-Substituted Anilines
    Substituent, Y pKa
    An arrow points upward; the bottom (blue) says weaker base, and the top (red) says stronger base. –NH2 6.15 Activating groups
    –OCH3 5.34
    –CH3 5.08
    –H 4.63  
    –Cl 3.98 Deactivating groups
    –Br 3.86
    –CN 1.74
    –NO2 1.00
    Exercise \(\PageIndex{1}\)

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