CEM2008S

Aromatic electrophilic substitution

Test your understanding of the topic

1 Explain how you would rank (arrange) the following set of compounds in order of increasing reactivity towards electrophilic aromatic substitution.

Nitration of the compound below gives a product with the proton NMR chemical shifts shown. Deduce the structure of the product from the NMR data and explain the position of substitution.
Hb Ha Ha Hb

CH3

.. : OH

HNO3

CO2H

NO2
The phenyl group, C6H5, is o,p directing

H2SO4

O2N

NO2

Hb

Ha Ha

Hb

Compound 1 is slightly activated due to the methyl group which is electron releasing, see arrow above. Compound 2 is an activated compound, one of the lone pairs on the oxygen atom can be delocalised into the ring. Both compounds 3 and 4 are deactivated aromatic compounds due to resonance forms which arise from the arrows in the structures shown below: Compound 4 is more strongly deactivating than 3 due to the positively charged nitrogen atom attached to the benzene ring.

There are 8 protons in the product, thus disubstitution has occurred, see 1 H NMR data.

H 7.77 (4Ha, d, J 10 Hz) H 8.26 (4Hb, d, J 10 Hz)

Note 1,4-disubstitution in aromatic compounds gives rise to a doublet of doublets (two doublets) in the 1H NMR spectrum particularly if the substituents are fairly strongly electron donating (phenyl) or strongly withdrawing (nitro) as in the case above. Thus Ha, which are adjacent to the phenyl group, are the more shielded protons, H 7.77. Hb which are adjacent to the nitro group are the more deshielded protons, H 8.26. 4 Electrophilic aromatic substitution can be an intramolecular reaction. Predict the product of the following reaction.

Order of reactivity is 4 < 3 < 1< 2

4 2 1 5 3

Cl

Predict the major product formed from the reaction of the following compound with one equivalent of Br2 and FeBr3 as a catalyst. Explain how you decided on your answer.
.. A

AlCl3

In this case the carbocation and benzene ring in the same molecule.

O
O H
O
2

CH2O ..

Br replaces this hydrogen atom

O
1 2 3

The use of one equivalent of the reagent implies that only one hydrogen atom will be replaced in the substitution reaction. This substance can be considered to be a combination of compounds 1 and 2 above in the same molecule. Thus ring B is more reactive. Substitution is more likely to take place on the para position in ring B as there is more steric crowding at the ortho position.
.

3 5 4
5 4

Note that in terms of the mechanism CO+ is equivalent to C=O.