Directing Aromatic Substituents Groups:

There are three positions on a benzene ring. This image outlines the different positiions.

These positions are important in naming benzene ring, since its ring structure makes numbering the carbons
complicated. Let's look at a specific molecule. We have a toluene molecule with some substituents here:

The bromine is ortho to toluene, while the chlorine is para to toluene. However, the positions don't really
matter in the naming of this specific compound. You would name this 1-bromo-3-chlorotoluene. The
ortho/para/meta directing is only important when synthesizing specific benzene-based rings. Certain
substituent groups can "direct" another substituent during certain reactions.

Directing Groups
The rate of substitution on a benzene ring is affected by what groups are already on the benzene ring. Those
groups which lower the rate of electrophilic substitution is calld an activating group. Any substituent that
lowers the rate (from benzene) of substitution is called a deactivating group.
An important thing to know about substitution reactions on benzene is that you will NEVER get exactly what
you want. You always get a mixture of what you want (a mixture of ortho/para/meta groups), and you must
then use methods to separate the stuff you don't want. For instance, you may want to substitute a nitro group
para from the the methyl group in the toluene. Once you have finished with the substitution reaction, only
37% of the final product will have the nitros in the para position. About 59% will have the nitro in the ortho
position, while 4% will have the nitro in the para group.
So when you plan out your substitutions, note what is on the benzene ring and remember that these groups
will DIRECT whatever substitution you want to a certain position.
Ortho-Para Directors

Strong
activato
rs

Meta Directors

Strong
deactivators

Modera
te
activato
rs

-NH2(amino)

-NO2 (nitro)

-OH (hydroxy)

-NR3(ammonium)

NHCOCH3(acetamide
)
Moderate
deactivators

OCOCH3(acetoxy)

-CN (cyano or nitrile)

-SO3H (sulfonic acid)

OR (alkoxy)
Weak
activato
rs

-CX3(trihalomethyl)

-CHO (aldehyde)

CH3(methyl)

-COR (ketone)

C6H5(phenyl)

-COOH (carboxyl)

Weakly Deactivating Ortho-Para directors

-F
(fluoro)

-Cl
(chloro)

-Br
(bromo)

-I
(iodo)

Why is this?
Well, electron-donating groups are activators and ortho-para directors because they stabilize the intermediate
cations. The intermediate cations are what is formed between the removal and addition stages. Electron
withdrawing groups are deactivators and met directors because they destabilize the intermediate cations. The
halogens, however, are a weird. Halogens are "special" and so they withdraw electrons, but can also provide
electrons if they are needed.

Try some exercises:

Where would the next group be directed?

We know that the nitro group is a strong deactivator, so it'll direct

meta. The next group would be on the meta postition.

The -OH group is strongly activating, so the final product will be mix
of ortho/para

The -Cl group is weakly deactivating, but directs ortho/para.

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