CHEM1280 Problem Set 9

(Due on 5 Dec., 2012)

1. a) Rank the following esters in order of decreasing reactivity in a nucleophilic acyl

substitution reaction:

b) Rank the following compounds in the decreasing order of reactivity toward the
reduction with NaBH4.

c) Rank the following compounds in the order of the decreasing reactivity toward the
nucleophilic acyl substitution with butylamine.

2. Given the products of the following reactions:

3. a) When a carboxylic acid is dissolved in isotopically labeled water (H2O18) in the

presence of an acid catalyst, the label is incorporated into both oxygens of the acid.
Propose a mechanism to account for this.

b) If a carboxylic acid is dissolved in isotopically labeled methanol (CH318OH) and an

acid catalyst is added, where will the label (18O) reside in the product?
4. An intramolecular Claisen condensation is called a Dieckmann condensation. Give the
mechanism for the following Dieckmann condensation.

5. Amantadine is effective in preventing infections caused by the influenza A virus and in

treating established illness. As shown below, amantadine is synthesized from
1-bromoadamantane in two steps.
(a) Propose a mechanism for the 1st step;
(b) Show suitable reagents to carry out the 2nd step.

6. Draw the Fischer projection for the following sugars in their open-chain forms:

7. Draw a furanose form of D-ribulose with a planar cyclic structure.

8. Propose a mechanism for the hydrolysis of sucrose to glucose and fructose in aqueous
acid using the curved arrows to show the flow of electrons.