19. Reactions of Aromatics: EAS and Beyond

What are the products of the following reactions?

f.

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.

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

a. (excess) benzene + isobutyl chloride + AlCl₃

List the compounds in each set from most reactive to least reactive toward electrophilic aromatic substitution:

b. dichloromethylbenzene, difluoromethylbenzene, toluene, chloromethylbenzene

Predict the product of the following multi-step synthesis.

What products are obtained from the reaction of the following compounds with one equivalent of Br₂, using FeBr₃ as a catalyst?

c.

d.

p-Xylene undergoes nitration much faster than benzene. Use resonance forms of the sigma complex to explain this accelerated rate

Predict the major products of the following reactions.

(b) phenol + tert-butyl chloride + AlCl₃

Predict the mononitration products of the following compounds.

d. p-methoxybenzoic acid

b. Rank the same compounds from greatest tendency to least tendency to undergo electrophilic aromatic substitution.

chlorobenzene, 1-chloro-2,4-dinitrobenzene, p-chloronitrobenzene

Predict the major products of bromination of the following compounds, using Br2 and FeBr3 in the dark.

(c)

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

(h) benzoyl chloride + AlCl₃

Draw the product(s) of each of the following reactions:

a. benzoic acid + HNO₃/H₂SO₄

b. isopropylbenzene + Cl₂ + FeCl₃

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

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

List the compounds in each set from most reactive to least reactive toward electrophilic aromatic substitution:

a. benzene, phenol, toluene, nitrobenzene, bromobenzene