Nitration of Methyl Benzoate

Pre Lab Assignment: Complete the pre-lab cover page and develop a procedure. Draw the
mechanism of the reaction you will complete in lab. Use the proper arrow drawing convention
to show all bond making and bond breaking steps in the reaction. Include all intermediates,
including resonance structures.
Learning Goals:
Introduce electrophilic aromatic substitution
Understand how substituent groups affect aromatic substitution
Introduction:
When an aromatic compound such as benzene reacts with an electrophile (E+), it undergoes an
electrophilic aromatic substitution reaction. The mechanism is shown below.
The electrophile accepts an electron from the pi system of the aromatic ring to form a resonance
stabilized carbocation.

Base
Resonance Stabilized Intermediates

When the electrophile is added to benzene, it can substitute onto any carbon in the ring. If a
substituent group is already present on the ring (a mono substituted aromatic system), it will
direct substitution to a specific carbon depending on whether the substituent is electron donating
or withdrawing. (Brown and Poon Pages 258-259)
In this experiment, you will be nitrating an aromatic ester. In most cases a Lewis acid catalyst
must be added to form an electrophile that is strong enough to undergo substitution. The
nitronium ion (NO2+) is the electrophile and it is generated by reacting nitric acid with sulfuric
acid (the catalyst) according to the following equilibrium reaction.
O

N
O

OH

S
O

O
OH

H2 O
N

OH2

N
O

HSO4

Because nitric acid alone does not provide a concentration of the ions that is sufficient for the
reaction to proceed at a significant rate, sulfuric acid is used as a proton source to generate a
higher concentration of nitronium ions at equilibrium.
The reaction between nitric acid and sulfuric acid is reversible, so adding water will reduce the
amount of nitronium ion, according to Le Chtliers principle. This will terminate the reaction.
Procedure:
Caution: Sulfuric and nitric acids are strong acids and can cause severe burns to skin on
contact. Nitric acid is a strong oxidant. It can rapidly oxidize organic materials: do not
put in contact with flammable materials. Nitric acid will also react with proteins (read:
skin) to stain the skin yellow: do not get nitric acid on skin. Wear gloves and avoid contact
with eyes, skin clothing, and other flammable materials. In case of contact with either
sulfuric or nitric acid, quickly wash the exposed surface with large amounts of water and
then report the issue to your TA.
Materials and supplies:
Stir plate
250 mL beaker containing ice and containing:
a 5 mL conical vial containing 560 L of sulfuric acid and spin vane,
a disposable test tube containing 240 L of nitric acid and 240 L of sulfuric acid,
a disposable test tube containing 200 L of methyl benzoate,
a disposable test tube containing 3 mL of deionized water, and
a disposable test tube containing 2 mL 1:1 methanol and water.
Obtain a stir plate from the stockroom and fill your beaker with crushed ice. Add 560 L of
sulfuric acid to a 5 mL conical vial containing a conical (triangular) spin vane and place in the
ice bath (beaker of crushed ice) for five minutes to cool. In a small disposable test tube, combine
240 L of nitric acid and 240 L of sulfuric acid and place this in your ice bath. Finally, add 3
mL of deionized water to a disposable test tube and place in the ice bath.
Remove your conical vial containing the sulfuric acid from the ice bath and clamp it above your
stir plate. While the acid solution is gently stirring, transfer the 200 L of methyl benzoate to the
conical vial dropwise using a Pasture pipette. After the addition of the methyl benzoate is
complete, add the cold nitric acid/sulfuric acid mixture to the conical vial again, dropwise. Let
the solution stir at room temperature for 15 minutes. After 15 minutes stop the reaction by
adding approximately 2 mL of de-ionized ice water. Using tweezers, carefully remove the spin
vane, and rinse the spin vane with the final 1 mL of cold water. Place the reaction solution in
your ice bath for 10 minutes. Stir the solution several times with a glass rod. You should see a
white precipitate (crystals!) forming once the solution cools. If the precipitate does not form,
wait a little longer and/ or get your TA.
Collect the precipitate using a Hirsch funnel (remember to clamp your funnel to the hood
structure and dont forget the filter paper!). Scrape any remaining product in the reaction vial

into your Hirsch funnel. Dissolve the remaining material in your reaction vial with
dichloromethane (~ 1 mL) for use in your TLC
With the crystals in the Hirsch funnel, rinse the crystals with 2 mL of a cold 1:1 methanol and
water solution and continue to pull a vacuum over the crystals for 5 minutes (this will remove the
excess methanol). Carefully place the filter paper containing your product in a beaker in your
drawer and allow to air dry for at least 24 hours. Dispose of all
liquid solutions in the sink with cold water.
Spot the known samples of methyl p-nitrobenzoate, mnitrobenzoate, and o-nitrobenzoate along side your reaction
sample (the material in the reaction vial that was dissolved in
dichloromethane) on a TLC plate and elute with 20 % ethyl
acetate/ 80% hexane. Which isomer, ortho, meta or para, do
you expect your product to be? Visualize the samples with UV
light and tape your TLC plate onto your report. If you cannot
unambiguously identify your product(s), run a co-spotted TLC
( lane 1: your reaction, lane 2: your reaction plus one of the
isomers, and lane 3: the isomer used in lane 2).

Temperature
Gauge

Come into the lab after 24 hrs have passed and weigh a vial.
Carefully scrape the product into the vial and re-weigh the vial.
The difference in weights is the weight of your product. After
you have weighed your product, calculate the percent yield and
determine the melting point of your product as was
demonstrated by your TA.

Post Lab:
Include what is required in the Lab Expectations handout.
Calculate your percent yield and determine the melting point. Put these calculations in
the calculations section of your report.
Address the following questions separately from your conclusion.
1. Is the ester group of your starting material electron donating or withdrawing?
Support your conclusion with resonance drawings.
2. Draw the mechanism of the nitronium ion reacting with the methylbenzoate.
3. Why does water stop the reaction?
4. According to your TLC plate, how many products did your reaction produce and
which isomers are produced?

Capillary tube
with product

Viewport

Temperature
Control