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16.8: Synthesis of Benzene Derivatives: Electrophilic Aromatic Substitution

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  • Bensene contains six pi electrons which are delocalized in six p orbitals above and below the plane of the benzene ring.

    The six pi electrons obey Huckel's rule so benzene is especially stable. This means that the aromatic ring want to be retained during reactions. Because of this benzene does not undergo addition like other unsaturated hydrocarbons.

    Benzene can undergo electrophilic aromatic substitution because aromaticity is maintained.


    The General Mechanism

    Step 1 (Slow)

    The e- in the pi bond attacks the electrophile

    One carbon gets a positive charge the other forms a C-E bond

    This forms the arenium ion.
    The arenium ion is conjugated but not aromatic.

    Step 2 (Fast)

    The LPE on a base attacks the hydrogen.

    This causes the e- in the C-H bond to form a C-C double bond and aromaticity is reformed

    A Detailed discussion of the Mechanism for Electrophilic Substitution Reactions of Benzene

    A two-step mechanism has been proposed for these electrophilic substitution reactions. In the first, slow or rate-determining, step the electrophile forms a sigma-bond to the benzene ring, generating a positively charged benzenonium intermediate. In the second, fast step, a proton is removed from this intermediate, yielding a substituted benzene ring. The following four-part illustration shows this mechanism for the bromination reaction. Also, an animated diagram may be viewed.

    bnzsub1.gif bnzsub2.gif

    Preliminary step: Formation of the strongly electrophilic bromine cation

    bnzsub3.gif enrdiag3.gif

    Step 1: The electrophile forms a sigma-bond to the benzene ring, generating a positively charged benzenonium intermediate

    bnzsub4.gif enrdiag4.gif

    Step 2: A proton is removed from this intermediate, yielding a substituted benzene ring

    This mechanism for electrophilic aromatic substitution should be considered in context with other mechanisms involving carbocation intermediates. These include SN1 and E1 reactions of alkyl halides, and Brønsted acid addition reactions of alkenes.

    To summarize, when carbocation intermediates are formed one can expect them to react further by one or more of the following modes:

    1. The cation may bond to a nucleophile to give a substitution or addition product.
    2. The cation may transfer a proton to a base, giving a double bond product.
    3. The cation may rearrange to a more stable carbocation, and then react by mode #1 or #2.

    SN1 and E1 reactions are respective examples of the first two modes of reaction. The second step of alkene addition reactions proceeds by the first mode, and any of these three reactions may exhibit molecular rearrangement if an initial unstable carbocation is formed. The carbocation intermediate in electrophilic aromatic substitution (the benzenonium ion) is stabilized by charge delocalization (resonance) so it is not subject to rearrangement. In principle it could react by either mode 1 or 2, but the energetic advantage of reforming an aromatic ring leads to exclusive reaction by mode 2 (ie. proton loss).

    Other Examples of Electophilic Aromatic Substitution

    Many other substitution reactions of benzene have been observed, the five most useful are listed below (chlorination and bromination are the most common halogenation reactions). Since the reagents and conditions employed in these reactions are electrophilic, these reactions are commonly referred to as Electrophilic Aromatic Substitution. The catalysts and co-reagents serve to generate the strong electrophilic species needed to effect the initial step of the substitution. The specific electrophile believed to function in each type of reaction is listed in the right hand column.

    Reaction Type Typical Equation Electrophile E(+)
    Halogenation: C6H6 + Cl2 & heat
    FeCl3 catalyst
    ——> C6H5Cl + HCl
    Cl(+) or Br(+)
    Nitration: C6H6 + HNO3 & heat
    H2SO4 catalyst
    ——> C6H5NO2 + H2O
    Sulfonation: C6H6 + H2SO4 + SO3
    & heat
    ——> C6H5SO3H + H2O
    Benzenesulfonic acid
    C6H6 + R-Cl & heat
    AlCl3 catalyst
    ——> C6H5-R + HCl
    An Arene
    C6H6 + RCOCl & heat
    AlCl3 catalyst
    ——> C6H5COR + HCl
    An Aryl Ketone


    • Prof. Steven Farmer (Sonoma State University)

    • William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry