Predict the major products of the following reactions.

(b) phenol + tert-butyl chloride + AlCl₃

Predict the major products of the following reactions.

(c) nitrobenzene + fuming sulfuric acid

Predict the major products of the following reactions.

(d) nitrobenzene + acetyl chloride + AlCl₃

Predict the major products of the following reactions.

(e) p-methylanisole + acetyl chloride + AlCl₃

Predict the major products of the following reactions.

(f) p-methylanisole + Br₂ , light

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

(a)

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

(b)

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

(c)

What products would you expect from the following coupling reactions?

(a)

What products would you expect from the following coupling reactions?

(b)

What products would you expect from the following coupling reactions?

(c)

What products would you expect from the following coupling reactions?

(d)

(e)

A student added 3-phenylpropanoic acid (PhCH₂CH₂COOH) to a molten salt consisting of a 1:1 mixture of NaCl and AlCl₃ maintained at 170 °C. After 5 minutes, he poured the molten mixture into water and extracted it into dichloromethane. Evaporation of the dichloromethane gave a 96% yield of the product whose spectra follow. The mass spectrum of the product shows a molecular ion at m/z 132. What is the product?

<IMAGE>

Give the structures of compounds A through B in the following series of reactions.

Give the structures of compounds A through C in the following series of reactions.

Give the structures of compounds C through D in the following series of reactions.

The following compound reacts with a hot, concentrated solution of NaOH (in a sealed tube) to give a mixture of two products. Propose structures for these products, and give a mechanism to account for their formation.

Show the products you expect when each compound reacts with NBS with light shining on the reaction.

(d)

α-Tetralone undergoes Birch reduction to give an excellent yield of a single product. Predict the structure of the product, and propose a mechanism for its formation.

Electrophilic aromatic substitution usually occurs at the 1-position of naphthalene, also called the a position. Predict the major products of the reactions of naphthalene with the following reagents.

(a) HNO₃, H₂SO₄

(b) Br₂, FeBr₃

(c) CH₃CH₂COCl, AlCl₃

Electrophilic aromatic substitution usually occurs at the 1-position of naphthalene, also called the a position. Predict the major products of the reactions of naphthalene with the following reagents.

(d) isobutylene and HF

Electrophilic aromatic substitution usually occurs at the 1-position of naphthalene, also called the 1-position. Predict the major products of the reactions of naphthalene with the following reagents.

(e) cyclohexanol and BF₃

The most common selective herbicide for killing broadleaf weeds is 2,4-dichlorophenoxyacetic acid (2,4-D). Show how you would synthesize 2,4-D from benzene, chloroacetic acid (ClCH₂COOH), and any necessary reagents and solvents.

Furan undergoes electrophilic aromatic substitution more readily than benzene; mild reagents and conditions are sufficient. For example, furan reacts with bromine to give 2-bromofuran.

a. Propose mechanisms for the bromination of furan at the 2-position and at the 3-position. Draw the resonance forms of each sigma complex, and compare their stabilities.

Furan undergoes electrophilic aromatic substitution more readily than benzene; mild reagents and conditions are sufficient. For example, furan reacts with bromine to give 2-bromofuran.

b. Explain why furan undergoes bromination (and other electrophilic aromatic substitutions) primarily at the 2-position.

(a) Draw the three isomers of benzenedicarboxylic acid.

(b) The isomers have melting points of 210 °C, 343 °C, and 427 °C. Nitration of the isomers at all possible positions was once used to determine their structures. The isomer that melts at 210 °C gives two mononitro isomers. The isomer that melts at 343 °C gives three mononitro isomers. The isomer that melts at 427 °C gives only one mononitro isomer. Show which isomer has which melting point.

Unlike most other electrophilic aromatic substitutions, sulfonation is often reversible (see Section 17-4). When one sample of toluene is sulfonated at 0 °C and another sample is sulfonated at 100 °C, the following ratios of substitution products result:

a. Explain the change in the product ratios when the temperature is increased.

b. Predict what will happen when the product mixture from the reaction at 0 °C is heated to 100 °C.

Unlike most other electrophilic aromatic substitutions, sulfonation is often reversible (see Section 17-4). When one sample of toluene is sulfonated at 0 °C and another sample is sulfonated at 100 °C, the following ratios of substitution products result:

c. Because the SO₃H group can be added to a benzene ring and removed later, it is sometimes called a blocking group. Show how 2,6-dibromotoluene can be made from toluene using sulfonation and desulfonation as intermediate steps in the synthesis.

In Chapter 14, we saw that Agent Orange contains (2,4,5-trichlorophenoxy) acetic acid, called 2,4,5-T. This compound is synthesized by the partial reaction of 1,2,4,5-tetrachlorobenzene with sodium hydroxide, followed by reaction with sodium chloroacetate, ClCH₂CO₂Na.

a. Draw the structures of these compounds, and write equations for these reactions.

Phenol reacts with three equivalents of bromine in CCl₄ (in the dark) to give a product of formula C₆H₃OBr₃. When this product is added to bromine water, a yellow solid of molecular formula C₆H₂OBr₄ precipitates out of the solution. The IR spectrum of the yellow precipitate shows a strong absorption (much like that of a quinone) around 1680 cm^–1. Propose structures for the two products.