Scribd Logo
Upload

Welcome to Scribd!

  • 874 views

    Aromatic Hydrocarbons

    Uploaded by

    api-3734333
    1) Benzene has a ring structure of six carbon atoms with alternating single and double bonds. Its stability is due to resonance and delocalization of π electrons across the entire ring. 2) Kekulé proposed the structure of benzene in 1865 based on evidence that there are three disubstituted isomers of dichlorobenzene. 3) Electrophilic aromatic substitution reactions involve attack of an electrophile on the π electron cloud of benzene, forming an intermediate arenium ion that loses a proton. Common electrophiles include nitration, halogenation, sulfonation and alkylation.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd

    Aromatic Hydrocarbons

    Uploaded by

    api-3734333
    874 views18 pages
    1) Benzene has a ring structure of six carbon atoms with alternating single and double bonds. Its stability is due to resonance and delocalization of π electrons across the entire ring. 2) Kekulé proposed the structure of benzene in 1865 based on evidence that there are three disubstituted isomers of dichlorobenzene. 3) Electrophilic aromatic substitution reactions involve attack of an electrophile on the π electron cloud of benzene, forming an intermediate arenium ion that loses a proton. Common electrophiles include nitration, halogenation, sulfonation and alkylation.

    Copyright

    © Attribution Non-Commercial (BY-NC)

    Available Formats

    PPT, PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    1) Benzene has a ring structure of six carbon atoms with alternating single and double bonds. Its stability is due to resonance and delocalization of π electrons across the entire ring. 2) Kekulé proposed the structure of benzene in 1865 based on evidence that there are three disubstituted isomers of dichlorobenzene. 3) Electrophilic aromatic substitution reactions involve attack of an electrophile on the π electron cloud of benzene, forming an intermediate arenium ion that loses a proton. Common electrophiles include nitration, halogenation, sulfonation and alkylation.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    874 views18 pages

    Aromatic Hydrocarbons

    Uploaded by

    api-3734333
    1) Benzene has a ring structure of six carbon atoms with alternating single and double bonds. Its stability is due to resonance and delocalization of π electrons across the entire ring. 2) Kekulé proposed the structure of benzene in 1865 based on evidence that there are three disubstituted isomers of dichlorobenzene. 3) Electrophilic aromatic substitution reactions involve attack of an electrophile on the π electron cloud of benzene, forming an intermediate arenium ion that loses a proton. Common electrophiles include nitration, halogenation, sulfonation and alkylation.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 18

    Aromatic Hydrocarbons

    (Chapter 32)
    Aromatic Hydrocarbons
    Aroma

    Ring of sp2 carbon atoms

    (4n+2) π delocalized bonding electrons


    CH3

    Benzene Methylbenzene Napthalene


    Discovery of the structure of
    benzene
    Molecular Formula: C6H6
    Structural Formula: ?

    Possible structure:
    A CH2=CH-C≡C-CH=CH2
    B CH3-C≡C-C≡C-CH3

    A is ruled out because only ONE


    monosubstituted chlorobenzene.
    Discovery of the structure of
    benzene

    Evidence: There are THREE disubstituted


    isomers of C6H4Cl2.

    B (CH3-C≡C-C≡C-CH3 )is ruled out too!


    Discovery of the structure of
    benzene
    Kekule(1865): Chemist and Dreamer

    …… one of the snakes has seized hold


    of its own tail …….

    Cl Cl
    H Cl
    H C H
    C C Cl
    C C
    H C H Cl
    Cl
    H
    Discovery of the structure of
    benzene

    Objections to Kekule Benzene:

    •A 4th isomer of C6H4Cl2


    •Surprising stability of benzene
    •All the C-C bonds are the same length
    Discovery of the structure of
    benzene
    Delocalization of Bonding
    Electrons

    •3e- in sp2 hybrids form


    normal covalent bonds
    •4th e-, one from each carbon
    atoms are free to visit
    all the atoms on the ring Delocalized π-bond system
    (delocalized bonding
    electrons)
    Stability of the Benzene Ring
    Enthalpy
    kJ/mol Resonance
    Energy
    150.4
    -358.8
    -208.4
    Cyclohexane

    Reaction co-ordinate
    Reactions of Benzene

    •No reaction with Br2/dark


    •No reaction with MnO4-/H+

    Benzene

    Although benzene is unsaturated,


    it is resistant to oxidation and addition reaction
    because of the energy of delocalization is lost
    in such reaction.
    Electrophilic Aromatic
    Substitution
    General Mechanism:
    •Formation of Electrophile, E+
    •Attack of E+ on π electron cloud of benzene
    •Loss of a proton

    r.d.s H -H+
    E+ E
    E
    +
    Benzenonium ion

    +
    H H H
    +
    E E E
    +

    H
    OR +
    E

    sp3
    Electrophilic Aromatic
    Substitution

    H
    H
    E
    +

    + E+
    E
    +H+

    Reaction coordinate
    Electrophilic Aromatic
    Substitution

    Reaction Reagent Catalyst Product E+ or E

    Halogenation X2(Cl,Br) FeX3 ArCl, ArBr X+

    Nitration HNO3 H2SO4 ArNO2 NO2


    +

    Sulphonation H2SO4 None ArSO3H SO3

    Alkylation RX(Cl,Br) AlX3 Ar-R R+


    Formation of E+

    • X2 + FeX3 => X+ + FeX4-


    • H2SO4 + HONO2 => HSO4- + H2O+NO2 =>
    H2O + +NO2
    • 2H2SO4 => HSO4- + H3O+ + SO3
    • RX + AlX3 => R+ + AlX4-
    Reversible nature of sulphonation

    SO3H
    c.H2SO4
    80oC, reflux
    Benzenesulphonic acid

    SO3H
    H2O, H2SO4 + H2SO4
    T>100oC
    Eact ≈ Eact*

    H
    H
    SO3-
    +

    + SO3
    SO3-
    +H+

    Reaction coordinate

    k-1 H k2
    ArH + SO3  Ar+ - → ArSO3 + H k-1 ≈ k2
    - +
    k1 SO3
    Oxidation of alkylbenzene
    CH3 COO- COOH

    KMnO4/OH- H3O+
    heat

    KMnO4/OH- is better than KMnO4/H+


    As C6H5COO- acts as a solvent that mix
    C6H5CH3 and MnO4-
    Oxidation of alkylbenzene
    Oxidation takes place at first by the abstraction
    of a phenylmethyl hydrogen by the O.A., once
    take place, oxidation continues until a
    carboxyl group is left.
    CH2CH2CH2R COOH

    CR3
    No reaction (no H on C)

    You might also like