19. Reactions of Aromatics: EAS and Beyond

Predict the mononitration products of the following compounds.

a. o-nitrotoluene

b. m-chlorotoluene

c. o-bromobenzoic acid

Give the products, if any, of each of the following reactions:

a. benzonitrile + methyl chloride + AlCl₃

b. phenol + Br₂

Give the products, if any, of each of the following reactions:

c. benzoic acid + CH₃CH₂Cl + AlCl₃

d. benzene + 2 CH₃Cl + AlCl₃

Predict the major products formed when benzene reacts (just once) with the following reagents.

(g) 1-chloro-2,2-dimethylpropane + AlCl₃

Propose products (if any) and mechanisms for the following AlCl₃-catalyzed reactions:

c. 3-chloro-2,2-dimethylbutane with isopropylbenzene

Predict the products (if any) of the following reactions.

a. (excess) benzene + isobutyl chloride + AlCl₃

Predict the products (if any) of the following reactions.

b. (excess) toluene + butan-1-ol + BF₃

Which reactions will produce the desired product in good yield? You may assume that aluminum chloride is added as a catalyst in each case. For the reactions that will not give a good yield of the desired product, predict the major products.

(d) Reagents: benzamide (PhCONH₂) + CH₃CH₂Cl

Desired Product: p-ethylbenzamide

Which reactions will produce the desired product in good yield? You may assume that aluminum chloride is added as a catalyst in each case. For the reactions that will not give a good yield of the desired product, predict the major products.

(e) Reagents: toluene + HNO₃, H₂SO₄, heat

Desired Product: 2,4,6-trinitrotoluene (TNT)

Predict the major products formed when benzene reacts (just once) with the following reagents.

(h) benzoyl chloride + AlCl₃

Predict the product(s) of the following reactions.

(d)

Predict the major products formed when benzene reacts (just once) with the following reagents.

e. isobutylene + HF

Predict the major products of the following reactions.

(a) 2,4-dinitrochlorobenzene + NaOCH₃

Predict the major products of the following reactions.

(c) nitrobenzene + fuming sulfuric acid

In Chapter 23, we learned about the electrophilic aromatic nitration reaction. When phenol is subjected to these conditions with a large excess of nitric acid, a molecule called picric acid is produced. Predict the product of this reaction and explain why the pK_a value of this compound is 0.38.