Massachusetts Institute of Technology 5.

13, Fall 2006

Problem Set #6
Due: November 13, 2006, 12:00 PM

1. Show how you would accomplish the following syntheses in good yields.

NH2
H
N H
a)

O
HO CH2NH2
b)

2. Propose a synthetic sequence to convert the given lactone into the following
amine.

HO
O
N
O

3. Show how you would synthesize chlorpheniramine, a powerful antihistamine

used in several decongestants, from the given carboxylic acid.

O
N
N OH N

Cl Cl

Massachusetts Institute of Technology 5.13, Fall 2006

4. Show how you would carry out the following transformation in which the ester
function at the lower left of the molecule is converted into a hydroxy group but the
one at the upper right is preserved.

OCH3 OCH3
H3 C H3 C
O O

H3 C O HO

5. Propose reasonable mechanisms for the following reactions.

O
H2 O H3O+/H2O +
a) Ph C N + PhMgI A NH4+
Ph Ph

O O
OH H3O+/H2O
b) O
OH

O O

6. a) When methanol containing an oxygen-18 isotope is treated with

benzenesulfonyl chloride in pyridine, a product A is formed. When A is treated
with sodium hydroxide, methanol is formed again along with another product B,
and the methanol contains none of the isotope. Identify products A and B.

O
pyridine NaOH
CH3OH
* + Ph S Cl A CH3OH + B
O

b) When methanol containing an oxygen-18 isotope is treated with acetyl

chloride in pyridine, a product C is formed. When C is treated with sodium
hydroxide, methanol is formed again along with another product C, and the
methanol contains all of the isotope. Identify the products C and D.

O
pyridine NaOH
CH3OH
* + H3C C Cl C * + D
CH3OH