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    Aromatic Notes 2 PDF

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    Chris_Barber09
    1. Electrophilic aromatic substitution reactions involve the attack of an electrophile on an aromatic ring, such as bromination using FeBr3. Different catalysts are used for chlorination and iodination. 2. Nitration uses the nitronium ion as the electrophile and forms a nitro group. Sulfonation uses sulfur trioxide to form a sulfonic acid group. 3. Friedel-Crafts reactions alkylate and acylate aromatic rings. Alkylation is limited by rearrangements while acylation favors the acylated product. Substituents activate or deactivate the ring.

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    Aromatic Notes 2 PDF

    Uploaded by

    Chris_Barber09
    153 views6 pages
    1. Electrophilic aromatic substitution reactions involve the attack of an electrophile on an aromatic ring, such as bromination using FeBr3. Different catalysts are used for chlorination and iodination. 2. Nitration uses the nitronium ion as the electrophile and forms a nitro group. Sulfonation uses sulfur trioxide to form a sulfonic acid group. 3. Friedel-Crafts reactions alkylate and acylate aromatic rings. Alkylation is limited by rearrangements while acylation favors the acylated product. Substituents activate or deactivate the ring.

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    Organic Chemistry

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    Aromatic Notes 2.PDF

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    1. Electrophilic aromatic substitution reactions involve the attack of an electrophile on an aromatic ring, such as bromination using FeBr3. Different catalysts are used for chlorination and iodination. 2. Nitration uses the nitronium ion as the electrophile and forms a nitro group. Sulfonation uses sulfur trioxide to form a sulfonic acid group. 3. Friedel-Crafts reactions alkylate and acylate aromatic rings. Alkylation is limited by rearrangements while acylation favors the acylated product. Substituents activate or deactivate the ring.

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    153 views6 pages

    Aromatic Notes 2 PDF

    Uploaded by

    Chris_Barber09
    1. Electrophilic aromatic substitution reactions involve the attack of an electrophile on an aromatic ring, such as bromination using FeBr3. Different catalysts are used for chlorination and iodination. 2. Nitration uses the nitronium ion as the electrophile and forms a nitro group. Sulfonation uses sulfur trioxide to form a sulfonic acid group. 3. Friedel-Crafts reactions alkylate and acylate aromatic rings. Alkylation is limited by rearrangements while acylation favors the acylated product. Substituents activate or deactivate the ring.

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    of 6

    Electrophilc Aromatic Substitution

    Resonance Structures

    Bromination

    Br

    Br

    FeBr3

    Br

    Br

    Br

    -electrophilic attack on aromatic ring


    -resonance structures stabalize intermediate
    -aromaticity is restored in the product
    Br

    -HBr

    FeBr4
    Br

    Aromatic chloronation and iodonation happen in the same manner but use different lewis acid catalysts:
    FeCl3 and CuCl2 respectively.
    Aromatic Nitration
    begins with formation of the nitronium ion: +NO2
    O

    O
    N

    H2SO4

    O
    H

    H
    N

    -H2O

    nitronium ion
    (electrophile)

    H2O
    O

    NO2

    N
    O

    Remember: Reduction of a nitro group to form an amino group


    NO2

    SnCl2, H3O

    NH2

    NO2

    H3O

    Aromatic Sulfonation
    useful for sufonation, protecting group and as an intermediate to phenols
    O

    H2SO4

    OH

    HSO4

    sulfer trioxide

    base
    H
    O

    SO3H

    SO3H

    S
    OH

    Remember: alkali fusion to produce phenol


    OH

    SO3H

    NaOH, high heat


    H3O

    Note: the alkali fusion reaction requires harsh


    solvent free conditions, therefore it is typically
    only useful with alkyl goups present on the ring

    Friedel-Crafts Alkylation
    problems/limiations
    -prone to carbocation rearrangements
    -will not work on an aromatic ring with electron withdrawing groups or amino groups
    -poly-alkylation certain to occur

    Cl

    AlCl3

    AlCl4

    AlCl4
    HCl

    AlCl3

    These are examples of alkyl halides that can rearrange:


    Cl

    Cl

    Cl

    Cl

    Friedel-Crafts acylation reaction


    Acid chloride can be made from a carboxylic acid and SOCl2
    resonance stabilized acyl cation
    O

    AlCl3
    R

    O
    attacting
    electrophile
    species

    Cl

    AlCl4

    HCl
    AlCl3

    Acylation does not occur more than once since the acylated product is less reactive than the starting material,
    due to the electron withdrawing nature of the group.
    Substituent Effects in Substituted Aromatic Rings
    The substitutents on an aromatic ring determine the reactivity of the aromatic substrate in subsequent reactions
    (either activating or deactivating). Examples:
    They will also direct the incoming reagent to a specific site on the ring (either ortho/para or meta).

    Deactivators/Meta Directors: EWG

    N
    NR3

    NO2

    Activators/Ortho-Para Directors: EDG

    R
    R

    OR

    R=any alkyl group or H

    R=any alkyl group or H

    Dectivators/Ortho-Para Directors: EWG


    F

    Cl

    Br

    OH

    HN

    Reactivity and directing ability in electrophilic aromatic substitutions are controlled by inductive effects and
    resonance.
    Inductive Effect-withdrawal or donation of electrons (electron density) through bonds. This is a result of a
    polarization in electronegativity.
    Resonance Effect-withdrawal or donation of electrons through bonds. Resonance structures can be drawn to
    explain the placement of electron density.
    General Structures:
    Electron-withdrawing groups(EWG):
    Y

    Electron-donating groups(EDG):

    Z is a more electronegative atom then Y

    Y is an electronegative atom

    destabalize the intermediate carbocation


    therefore the ring is less reactive

    stabalize the intermediate carbocation


    therefore the ring is more reactive

    Halogens, despite the fact that they are electron-donating groups, deactivate the ring since they have stronger
    electron-withdrawing capabilities.
    Resonance Structures for electron-donating groups show that the most stable electrophilic attacks take place
    in the ortho and para positions; electron-withdrawing groups show that the most stable elctrophlic attacks
    take place in the meta postion.
    Trisubstituted Benzene: Considerations of Different Effects
    1. If two directing groups direct to the same place then the incoming reagent will react in this position.
    Br
    HO

    NO2

    Br2
    FeBr3

    HO

    NO2

    2. If two groups oppose each other then the more powerful activating group has the major influence. Often a
    mixture of products results.
    Br

    HO

    CH3

    Br2
    FeBr3

    HO

    CH3

    3. If two groups are meta to one another they are usually two bulky to allow attack between them. The
    incoming reagent will be directed to another site on the ring.
    CH3

    CH3
    HO

    Br2
    FeBr3

    HO

    CH3
    HO

    Br

    Br

    Nucleophilic Aromatic Substitution


    Only takes place on electron deficient rings! EWG must be present!
    Proceed through an addition/elimination mechanism
    Cl

    Cl
    O2N

    NO2

    O2N

    OH

    NO2

    OH

    OH
    O2N

    NO2

    NO2

    NO2

    NO2

    extremely electron
    deficient ring

    Benzyne: Triple bond in an aromatic ring.


    Strong base (either OH or NH2) eliminates HX (via an E2 mechanism) where X is Cl or Br producing
    benzyne. Benzyne is then subject to a nucleophilic attack as well as other reactions such as Diels-Alder
    NH2

    NH3
    NH2

    Cl

    CH3

    CH3

    OH

    CH3

    CH3

    Br

    CH3

    CH3
    OH

    H2O

    OH

    OH

    Oxidation of alkylbenzene side chains to carboxylic acids.


    Must have a benzylic proton. Tert-butyl won't react!
    CHR2

    KMnO4
    H2O

    where R=H or alkyl

    COOH

    KMnO4
    H2O

    N.R.

    Bromination of Alkylbenzene Side Chains


    Radical mechanism, benzylic radical very stable, typical initiation, propogation, termination steps.
    Br

    Br

    NBS

    Br

    Reduction with aromatic rings


    Hydrogen with Pd or Pt catalysts won't reduce aromatic rings or non-benzylic carbonyls.
    O

    H2, Pd

    It will reduce aryl alkyl ketones to alkanes and aromatic nitro groups to amino groups
    O

    H2, Pd

    O2N

    H2N

    Clemmensen Reduction will reduce all carbonyls, it will also reduce aromatic nitro groups to amino groups
    O

    Zn(Hg)
    HCl

    Hydrogen with Rhodium Catalyst will reduce the aromatic ring to cyclohexane
    H2, Rh/C

    Protecting Groups for Synthesis: put in a place holder group so the position it occupies is not attacked.
    tert-butyl
    sulfonate
    Cl

    Br2
    HCl

    Cl

    Cl

    FeBr3

    SO3

    HNO3

    H2SO4

    H2SO4
    SO3H

    SO3H
    Cl

    Br

    HCl
    AlCl3

    Br

    NH2

    SnCl2, H3O
    -OH
    SO3H

    NO2

    Cl

    H3O

    NH2

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