CHEM 351

Spring 2002

Principles of Organic Chemistry II Laboratory

Prof. Nalli
WSU

Experiment #6. Nucleophilic Aromatic Substitution: Reaction of an Arenediazonium Salts

with Iodide1
Relevant Reading: Bruice, chap 15.10-15.12. Williamson, chap 45.
Overview
Arenediazonium salts (ArN2+Y) are very useful for the synthesis of compounds, such as
iodoarenes (ArI), which are not easily available from direct electrophilic aromatic substitution
reactions. The diazonio group (N2+) is a super leaving group and allows nucleophilic aromatic
substitution by nucleophiles such as the iodide ion (eq 1).
+

Ar-NN:

I:

Ar-I

:NN:

(1)

The diazonium salt can be prepared using sodium nitrite and sulfuric acid from the
corresponding aromatic amine in a process termed "diazotization" (eq 2).
Ar-NH2 +

NaNO2 + 2 H2SO4

ArN2+HSO4 + 2 H2O + NaHSO4 (2)

In this experiment you will carry out the diazotization of p-nitroaniline. The resulting
p-nitrobenzenediazonium salt solution will be reacted with aqueous potassium iodide to form
p-iodonitrobenzene. An NMR spectrum of the product will be obtained.
Procedures
1. Diazotization of p-Nitroaniline. Dissolve 1.0 mL H2SO4(conc) in 10 mL H2O in a 50mL Erlenmeyer flask. Swirl the solution while adding 1.0 g p-nitroaniline. Chill the mixture on an
ice bath. Prepare a solution of 0.5 g NaNO2 in 4 mL H2O. After the temperature of the
p-nitroaniline-H2SO4 solution has reached about 5C begin a slow addition of the NaNO2 solution.
(Use a Pasteur pipet to add the solution one drop at a time.) The rate of addition should be slow
enough so that the temperature of the reaction mixture never exceeds 10C. (Above this
temperature the diazonium salt undergoes nucleophilic substitution by H2O resulting in phenol
formation.) Keep the solution on an ice bath until use in the subsequent parts of this experiment.
2. Preparation of p-Iodonitrobenzene. Prepare a solution of 3.0 g KI in 30 mL H2O.
Transfer the diazonium solution from part 1 to a large flask. Use a Pasteur pipet to slowly add the
KI solution to the diazonium solution, swirling constantly. (Note the evolution of nitrogen gas
from the reaction mixture.) Collect the precipitate by vacuum filtration and wash it with a 2-3 mL
of cold water. Recrystallize the product from 95% ethanol (using activated charcoal to decolorize
the hot solution if necessary) and allow it to air dry in your lab drawer for one week. Weigh the
dried product, measure the mp and obtain an NMR spectrum. Put the product in a labeled in a
Adapted from; Mohrig, J. R.; Hammond, C. N.; Morrill, T. C.; Neckers, D. C. Experimental
Organic Chemistry. A Balanced Approach: Macroscale and Microscale; W. H. Freeman: New York,
1997.
1

small zip-loc bag and attach to your report.

Report - This is a short write-up lab. However, remember to include the following in your report for
this experiment.
(1) A Results Table with the theoretical yield, actual yield and % yield of the iodoarene product of
part 2. (Because the diazonium salt prepared in part 1 is not isolated, it is impossible to give a
percent yield for this part. You should assume a 100% yield for part 1 in calculating the theoretical
yields for part 2.) Also give the experimental and literature mp present the experimental NMR data
obtained on the product and give a comparison to literature values for the NMR of this compound.
(2) Attach the NMR spectrum of p-iodonitrobenzene with all peaks assigned and any proton count
measurements clearly shown. (As usual the spectrum should also be completely labeled with your
name, date, experimental parameters, etc.)