Electrophilic aromatic directing groups

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In organic chemistry, an electron donating group (EDG) or electron releasing group (ERG) is an atom or functional group that donates some of its electron density into a conjugated π system via resonance or inductive electron withdrawal, thus making the π system more nucleophilic.[1][2] When attached to a benzene molecule, an electron donating group makes it more likely to participate in electrophilic substitution reactions. Benzene itself will normally undergo substitutions by electrophiles, but additional substituents can alter the reaction rate or products by electronically or sterically affecting the interaction of the two reactants. EDGs are often known as activating groups.

An electron withdrawing group (EWG) will have the opposite effect on nucleophilicity as an EDG, as it removes electron density from a π system, making the π system more electrophilic.[2][3] When attached to a benzene molecule an electron withdrawing group makes electrophilic aromatic substitution reactions slower and more complex, and EWGs are often called deactivating groups. Depending on their relative strengths, EWGs also determine the positions (relative to themselves) on the benzene ring where substitutions must take place; this property is therefore important in processes of organic synthesis.

Electron donating groups are generally ortho/para directors for electrophilic aromatic substitutions, while electron withdrawing groups are generally meta directors with the exception of the halogens which are also ortho/para directors as they have lone pairs of electrons that are shared with the aromatic ring.

Categories[edit]

Electron donating groups are typically divided into three levels of activating ability. Electron withdrawing groups are assigned to similar groupings. Weakly deactivating groups direct electrophiles to attack the benzene molecule at the ortho- and para- positions, while strongly and moderately deactivating groups direct attacks to the meta- position. This is not a case of favoring the meta- position like para- and ortho- directing functional groups, but rather disfavoring the para- and ortho- positions more than they disfavor the meta- position.

Strongly activating groups (electron donating)[edit]

  • -NH2
  • -NHR
  • -NR2
  • -OH
  • -O-

R = alkyl

Strongly activating substituents favor electrophilic substitution about the ortho and para positions.
This is illustrated by drawing the resonance structures of aniline: [1]

Moderately activating groups[edit]

  • -NHCOCH3
  • -NHCOR
  • -OCH3
  • -OR

Weakly activating groups[edit]

  • -CH3
  • -C2H5
  • -R
  • -C6H5

Moderately deactivating groups[edit]

-CN, cyano groups

-SO3H, sulfonates

-COOH, carboxylic acid

-COOR, esters

-CHO, -COR, aldehydes and ketones

Strongly deactivating groups (electron withdrawing)[edit]

-NO2, nitro groups

-NR3+ quaternary amine or quaternary ammonium base

-CF3, CCl3 trihalides

Halides are ortho- para- directing groups but unlike most ortho para directors halides tend to deactivate benzene. This unusual behavior can be explained by two properties: 1.) Since the halogens are very electronegative they cause inductive withdrawal ( withdrawal of electrons from the carbon atom of benzene) 2.) Since the halogens have non-bonding electrons they can donate electron density through pi bonding. ( resonance donation) The inductive and resonance properties compete with each other but overall the inductive wins and halogens as a result become deactivating ortho para directors. Fluorine directs strongly to the para position (86%) while Iodine directs to ortho and para (45% and 54% respectively).

Mechanism[edit]

While steric effects are a consideration, the major contribution of EWGs is achieved by utilizing the nature of conjugated systems (specifically the ease through which mesomeric effects travel through such systems) to create regions of positive charge within the resonance contributors. For example, in nitrobenzene the resonance structures have positive charges around the ring system:

Nitrobenzene resonance.svg

The resulting resonance hybrid, now possessing δ+ charges in the ortho- and para- positions repels approaching electrophiles increasing the relative success of attack in the meta position.

The selectivities observed with EDGs and EWGs were first described in 1892 and have been known as the Crum Brown–Gibson rule.[4][5]

See also[edit]

References[edit]

  1. ^ "Electron withdrawing group". Illustrated Glossary of Organic Chemistry. UCLA Department of Chemistry. Retrieved 16 November 2012. 
  2. ^ a b Hunt, Ian. "Substituent Effects". University of Calgary Department of Chemistry. Retrieved 16 November 2012. 
  3. ^ "Electron donating group". Illustrated Glossary of Organic Chemistry. UCLA Department of Chemistry. Retrieved 16 November 2012. 
  4. ^ Crum Brown, A.; Gibson, J. (1892). J. Chem. Soc. 61: 367. 
  5. ^ "Crum Brown–Gibson rule". www.chempensoftware.com. 5 February 2011. Retrieved 13 August 2014.