Ortho/Para and Meta-Directing Groups in EAS

EAS of a mono-substituted benzene can lead to 3 different products

R R E R R

EAS E
E Ortho/Para-Substitution Meta-Substitution E

Recall that protonation of an alkene occurs such that the more stable carbocation is generated. Similarly, regioselectivity in EAS reactions are directed by the relative stabilities of the carbocationic intermediates.

H Cl R Primary carbocation is NOT formed because it is less stable

Professor M. J. Krische, UT Austin

H R

Cl

H R Secondary carbocation IS formed because it is more stable

Ortho/Para and Meta-Directing Groups in EAS

Note that para-attack of the electrophile generates a more stable carbocationic intermediate than meta-attack. For this reason, para-attack is favored.

Professor M. J. Krische, UT Austin

Ortho/Para and Meta-Directing Groups in EAS

Note that para-attack of the electrophile generates a more stable carbocationic intermediate than meta-attack. For this reason, para-attack is favored.

Professor M. J. Krische, UT Austin

Ortho/Para and Meta-Directing Groups in EAS

Professor M. J. Krische, UT Austin

Ortho/Para and Meta-Directing Groups in EAS

Note: The methoxy and methyl groups are cation-stabilizing groups. In general, cationstabilizing groups are ortho/para-directors.
Professor M. J. Krische, UT Austin

Ortho/Para and Meta-Directing Groups in EAS

Now consider a benzene that is substituted with an electron withdrawing group. Note that meta-attack of the electrophile generates a more stable carbocationic intermediate than ortho- or para-attack.

Professor M. J. Krische, UT Austin

Ortho/Para and Meta-Directing Groups in EAS

Professor M. J. Krische, UT Austin

Ortho/Para and Meta-Directing Groups in EAS

Note: The nitro- and ester groups are cation-destabilizing groups. In general, cation-destabilizing groups are meta-directors.
Professor M. J. Krische, UT Austin

Ortho/Para and Meta-Directing Groups in EAS

Summary There are three types of directing groups
Ortho/Para-Directors that activate the ring toward addition. Functional groups in this category include: R (alkyl), NH2, NR2, NHCOR, OH, OR, and OCOR. Ortho/Para-Directors that deactivate the ring toward addition. Functional groups in this category include the halogens. Meta-Directors that deactivate the ring toward addition. Functional groups in this category include: NO2, SO3H and all carbonyl compounds: COOH, COOR, CHO, and COR.

In general:
All activating groups are Ortho/Para-Directors and are electrondonating. All deactivating groups are Meta-Directors and are electronwithdrawing. Any group with a lone pair of electrons adjacent to the ring is an Ortho/Para-Director
Professor M. J. Krische, UT Austin