TheEffectofSubstituentsonReactivityandOrientationinElectrophilicAromaticSubstitution

DrGerardMcGlacken
1.

Ortho/ParaDirectingandActivating
E.g.Aniline(alsolookatelectronicspriortoE+attack)

stabilised
resonance
form

NH2
E

E
H

NH2

NH2

E
H

E
H

NH2

NH2

/meta
E
H

NH2

E
H

/ortho

NH2
E

NH2

/para

NH2

E H

E
H

E
H
NH2

E H

NH2

E H

NH

E H

E.g.Toluene

2.

MetaDirectingandDeactivating
E.g.Benzaldehyde(AlsolookatelectronicspriortoE+attack)

E.g.CF3group


3.

Ortho/ParaDirectingyetDeactivating!Halogens(ElectronegativityofXdeactivatesbutX+more
stableresonanceformdirects)

X
stabilised
resonance
form

E
H

E
H

/meta
E
H

X
E
H

/ortho

X
E

E
H

E
H

E H

E H

E H

E H

/para

ClassificationofSubstituents:
Ortho,ParaDirectors
StronglyActivatingNH2NHRNR2OHOR
ModeratelyNHCOCH3NHCOROR
WeaklyActivatingCH3RC6H5
WeaklyDeactivatingFClBrIN=O
MetaDirectors
ModeratelydeactivatingCNSO3HCOOHCOORCHOCOR
StronglydeactivatingNO2N+R3CF3CCl3
OrderofReactivity

NH2>OH>OCH3>NHCOCH3>CH3(alkyl)>Ph>H>F>Cl>Br>I>CHO>COOCH3>COOH>COCH3>SO3H>CN
>NO2>CF3>N+R3

ThesenotesarenotareplacementforattendanceatLectures.

E
H