Textbook: Brown 6th Ed. (2011)

Individual Problems

Problem # 588

Let's draw resonance forms to see why some groups are EDG or EWG. (I've started you off)

Where are the positive or negative charges placed in EDG/EWG? (ortho/meta/para) Why would this affect EAS reactions?

Note: EDG = electron donating group, EWG = electron withdrawing group

Problem # 587

Use curved arrows to draw a mechanism for the generic electrophilic aromatic substitution (EAS) reaction below.

Problem # 596

Indicate the eletrophile formed by each set of reagents/conditions below.

Problem # 678

Draw the structure of the major organic product from each reaction sequence.

Problem # 611

Draw in the arrows to show the electron flow and resonance forms in the nucleophilic aromatic substitution reaction below.

Note: Depending on the textbook, nucleophilic aromatic substitution is referred to as NAS, SNAr, or addition-elimination.

Problem # 612

Draw a mechanism for the nucleophilic aromatic substitution (SNAr) reaction below. Show all resonance forms of the intermediate.

Problem # 615

Let's go through a benzyne reaction (also called elimination-addition).

In the reaction below, the strong base (NaNH2) will form a benzyne intermediate, which when forms either ortho nitroaniline or meta nitroaniline.

Used curved arrows to show the formation of each intermediate and the final products.

Problem # 589

-OR is an EDG and an ortho-para director. Let's draw an EAS reaction's cyclohexadienyl cation intermediates to demonstrate why this is true. I've started you off.

Problem # 590

-NO2 is an EWG and a meta director. Let's draw an EAS reaction's cyclohexadienyl cation intermediates to demonstrate why this is true. I've started you off.

Problem # 584

Imidazole (shown below) has two nitrogen atoms, N-1 and N-3. Which nitrogen is more basic?

To answer this problem, draw the product after each nitrogen protonates, and compare their stabilities. Explain your reasoning.

Problem # 591

Pyrrole undergoes eletrophilic aromatic substitution at C-2. Let's compare the resonance forms of EAS carbocation intermediates to see why this is the case. What do you think? Why C-2 and not C-3?

Problem # 595

Phenol can be prepared from benzene and hydrogen peroxide in the presence of a really strong acid. Propose a mechanism for this reaction.

Problem # 722

Show how to prepare vinyl benzene from benzene.

Problem # 616

Let's go through another way to make benzyne.

First, let's form a Grignard reagent. Then, let's elminate to form benzyne.

Problem # 592

Naphthalene undergoes eletrophilic substitution at C-1.

Why is this the case, even though substitution at C-2 gives more resonance forms?

Problem # 593

a) Rationalize the relative stabilities of the cation species below.

b) Pyridine undergoes eletrophilic substitution at C-3. Let's compare the resonance forms of EAS carbocation intermediates to see why this is the case. Consider part a) in your explanation.

Problem # 594

A chemist tried to prepare compound A from benzene via Friedel-Crafts alkylation and instead produced compound B.

Why did this happen? How could the chemist prepare compound A?