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    Orientation in Electrophilic Substitution Reactions On Benzene Ring

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    MohammadHussainKhan

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    Orientation in Electrophilic Substitution Reactions On Benzene Ring

    Uploaded by

    MohammadHussainKhan
    165 views4 pages

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    Orientation in Electrophilic Substitution Reactions on Benzene Ring

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    165 views4 pages

    Orientation in Electrophilic Substitution Reactions On Benzene Ring

    Uploaded by

    MohammadHussainKhan

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
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    ORIENTATION IN ELECTROPHILIC SUBSTITUTION REACTIONS

    ON BENZENE RING:
    Reactivity and Orientation of Benzene Ring: -
    Reactivity: -
    The electrophilic substitution reactions are not only characteristic of benzene but are
    also given by substituted benzenes. In electrophilic substitution reaction benzene ring provides
    electrons to form a bond with electrophilic. While a group is attached with benzene it will affect
    the reactivity of the ring (benzene). Thus, any substituent group on aromatic ring that causes an
    increase in the electrons density of the ring will increase the reactivity of the ring while a group
    that decreases the electron density of the ring will decrease the reactivity.
    Reactivity of the benzene ring in electrophilic substitution reactions depends upon the
    tendency of the substituent group already present in the benzene ring to release or withdraw
    electrons. Thus, there are two types of substituents.
    1. Activating Group or Ring Activators.
    2. Deactivating Groups or Ring Deactivators: -
    Activating Groups: -
    A substituent group that increases the reactivity of the aromatic ring relative to the
    benzene ring itself is called activating group or ring activator.

    Deactivating Groups: -
    The group that decreases the reactivity of the ring relative to benzene itself is called
    deactivating group or ring deactivator.
    Thus, an activating group makes the aromatic ring react faster than benzene and
    deactivating group makes the aromatic ring to react slower than benzene.

    Theory of Activation and Deactivation: -


    To understand why some substituents, make a benzene ring more reactive than benzene
    itself (ring activators) whereas other makes it less reactive (ring deactivator). Let us assume the
    rate determining step of the mechanism of electrophilic substitution reactions. The first step of
    electrophilic substitution of benzene ring is the formation carbocation. The more stable the
    carbocation, the lower in energy of the transition state that forms it and the faster the reaction.
    H
    E

    E+ Catalyst
    H
    The principles of inductive and resonance effects can now be used to predict the
    carbocation stabilities. Electrons donating groups stabilize the carbocation making reaction
    faster while electron with drawing the groups destabilize the carbocation making the reaction
    slower. In other words, the electrons donating groups activate a benzene ring and electron
    withdrawing group deactivates a benzene ring.
    E

    D H

    D = (donor group of electrons). The carbocation is more stable, substitution is faster, and
    ring is activated.
    E

    W H

    W = Electrons with drawing group making carbocation less stable and substitution is
    slower, and ring is deactivated.

    Electron donor group D stabilities the carbocation intermediate, lower the energy of the
    transition state and increase the rate of reaction.
    Electrons with drawing group W destabilize the carbocation intermediate raise the energy
    of the transition state and decrease the rate of reaction.
    All activators are either R group or they have an N or O atom with a lone pair directly
    bonded to the benzene ring. There is the electron donor group.
    Example: -
        
    − NH2 ,OH, −NHR, NR2 ,OR,
    
    NHCoR, R
    All the deactivators are either halogens or they have an atom with a partial or full
    positive charge bonded directly to the benzene ring. These are the electrons with drawing
    groups.
    e.g. +
        +
    −
    F ,−Cl ,−Br , −
    I , − CHO, − COR, − COOR, − COOH, CN2 , −SO3 H,−NO2 ,− NR3
    

    

    

    
     

    Orientation: -
    The determination of the position of a new incoming group in substituted derivatives of
    benzene is called orientation.
    When an electrophilic substitution reaction is carried out on benzene the substituent
    group may occupy any of the six available positions in the ring because all the six positions are
    equivalent and only one mono-substituted benzene is produced. However, the introduction of a
    second group into the ring may yield three isomeric disubstituted benzene depending on
    whether the second group enters a position of ortho, Meta and para to the first.
    X

    +X

    X
    Y
    +Y

    X X
    Y

    or

    Which of the three available positions (o, m, and p) is occupied by the second group is
    determined by the group already in the ring. In other words, the group already presents in the
    aromatic ring influence the orientation of the second group.
    The group already presents in the ring direct the incoming second group on to two
    positions.
    i. Ortho Para directions.
    ii. Meta Directions.
    Generally, the ortho-para directors activate a ring toward the electrophilic substitution
    whereas Meta directors (groups) deactivate a ring toward electrophilic substituents.

    Theory of Directing Groups: -


    To understand why particular orientation effect, arise. We must keep in mind the general
    structure for ortho, para directions and for Meta directors.
    All ortho-para directors are R group or have a non-bonded electron pair on the atom bonded to
    the benzene ring.
    Z
    R

    All meta directors have a full or partial positive charge on the bonded atom to the
    benzene ring(δ+ or+).
    Y

    −𝐶𝑁, 𝐶𝑂𝑂𝐻, 𝑆𝑂3 𝐻etc.


    The resonance theory clearly explains why certain substituents ortho-para directing and
    others are meta directing.
    The ortho-para directing groups release electrons to the benzene ring, in fact, the ortho
    and para directing groups increase the concentration of the negative charge at ortho and para
    position and make these positions attractive for the new electrophile.
    CH3 CH3 CH3
    NO2
    2HNO3 + H2SO4
    2 + + 2H2O

    NO2

    The electron releasing effect of methyl (CH3) group is significant.


    While meta directing group withdraw electrons from the benzene ring. The decrease in
    the electron density at ortho-para positions and hence new group comes to Meta direction
    where electrons density is not much effect by electrons with drawing group.
    NO2 NO2

    HNO3 + H2SO4
    95Co
    NO2

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