1.

How would you make each of the following compounds from

benzene?
• The first compound has a ketone substituent, Which is electron
withdrawing and therefore meta-directing. And an amino group,
Which is electron donating and therefore ortho, para-directing.
Aromatic amino groups are best made by reduction of nitro-groups,
Which are also meta-directing, So there are two possibilities. We can
either start with a Friedel-Crafts acylation of benzene to give the
ketone, Which we can nitrate in the meta position and then reduce,
or we can start by nitrating benzene, then do the acylation and then
reduce. Either is a reasonable solution.
• The second compound has a bromo substituent, which is ortho, para-
directing, and a meta-directing nitro-group. We need the para
relationship, so we must put the bromine in first, then nitrate.
• Finally, a compound with two para-directors arranged meta to one
another. This. May seem a problem, but we must introduce the alkyl
group by Friedel – Crafts acylation and reduction. since primary alkyl
groups cannot be introduced by Friedel – Crafts alkylation. The acyl
group will be meta-directing, so that solves both problems. First
acylate, then brominate , then reduce.
2. What are the two possible isomeric products of the reaction ? Which
structure do you expect to predominate? What would be the
bromination product from each?
The reaction is a Friedel-Crafts cyclization, as you could have deduced by
the simple loss of water. The resulting cation could cyclize in two ways,
arbitrarily called A and B. Steric hindrance suggests that A would be
the more likely product.
• Bromination will go either ortho or para to the methoxy group: A has
two different positions ortho to the OMe,but the para position is
blocked. The least sterically hindered position gives 1,2,4,5-
tetrasubstituted ring. B might give a mixture of ortho and para
substitution.
THANK YOU