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    CHE1122 Day7 8

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    CHE1122 Day7 8

    Uploaded by

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    CHE1122-Day7-8

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    2 views13 pages

    CHE1122 Day7 8

    Uploaded by

    nivarthana.ekanayaka

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    © All Rights Reserved
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    Download as pdf or txt
    of 13

    CHE 1122

    Organic Chemistry
    Aromaticity and
    Reactions of Aromatic Compounds

    Dr. Harshi Manawadu


    Senior Lecturer
    Department of Chemistry

    1
    Nucleophilic Aromatic Substitution
     Aromatic Substitution reactions usually occur by electrophilic
    aromatic substitution.
    Nu
    No Reaction

     However aryl halides with strong electron withdrawing substituents


    can under go nucleophilic aromatic substitution.
     Aryl halides with EWGs to –ortho and –para to halide undergo
    nucleophilic substitution.

     What is the mechanism ?????


     Aryl halides does not undergo substitution by SN1 or SN2
    mechanisms
     SN1 reaction:

     SN2 reaction:
    Addition/Elimination Mechanism
     Nucleophilic attack to the electron deficient aryl halide,
    forms a negatively charged intermediate called
    Meisenheimer complex.
    Addition :
     Elimination

     Nucleophilic displacement of groups other than halogen can also


    take place in the presence of EWG present
    Benzyne
     Halobenzene without EWGs as substituents are inert to nucleophiles
    under most conditions
     Phenol is prepared on an industrial scale by treatment of chlorobenzene
    with dilute aqueous NaOH at 340°C under high pressure.

     This reaction takes place by an elimination/addition mechanism.


     In this mechanism a strong base first causes the elimination of HX
    from halobenzene by E2 reaction, yielding a highly reactive benzyne
    intermediate.

     A nucleophile adds to benzyne in the second step to give the


    product.
    Evidence for benzyne formation
     Bromobenzene with 14C* only at C1 gives substitution product
    with label scrambled between C1 and C2

     Reaction proceeds through a symmetrical intermediate in which


    C1 & C2 are equivalent— a requirement met by benzyne
    Mechanism
    Cl
    Cl
    H *
    *
    *
    + NH2 +NH3 +Cl-

    NH2 NH2
    * *
    *
    H-NH2
    + NH2
    NH2

    * *
    Benzyne NH2 NH2
    H-NH2
    Structure of Benzyne
     Benzyne is a highly distorted alkyne
     The triple bond uses sp2-hybridized carbons, not the usual sp
     The triple bond has one π bond formed by p–p overlap and another by
    weak sp2–sp2 overlap
     Benzyne is too reactive and unstable.
     To further identify, it can be trapped by Diels-Alder reaction

    Br
    -NH2
    O

    NH3 (liq) O

    Benzyne Furan the product of the


    a dienophile a diene Diels - Alder
    reaction
    Refer :

    1. Reactions of alkyl benzenes


    2. Oxidation of substituted benzenes
    3. Reduction of benzenes and substituted benzenes

    Birch Reduction

    Na/NH3
    EtOH
    1,4-cyclohexadiene

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