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Amber Iverson
Department of Chemistry
Pacific Lutheran University
Tacoma, WA 98447
iversoai@plu.edu
Submitted 11/22/2006
experiment the goal was to successful add a nitro group to methyl benzoate using nitric acid
and sulfuric acid as a reagents, and vacuum filtration and centrifugation for isolation. The
percent yield from the original reagents was 26%, and the nitro group was successfully
added to the aromatic structure, which can be seen in the IR spectra of the final product.
Introduction:
nitro (NO2) group is being substituted for a hydrogen on an aromatic compound. This is
achieved by the formation of the nitronium ion via protonation of nitric acid from sulfuric
acid. The nitronium ion is a strong enough electrophile, and can react with the aromatic
compound (in this experiment Methyl benzoate) to form an arenium ion intermediate. The
arenium ion is then deprotonated to reform the aromatic ring and yield the final product
Aromatic substitution reactions are important synthetic reactions that are used to
(more commonly known as aspirin). In a study published in 2001 in the Journal of the
American Chemical Society, aromatic ether linkages can be effectively created using
ether linkages that are found in nature and can be synthesized using aromatic substitution.
The most common use of polyarylene ethers are in high-performance engineering plastics.
carbon dioxide is used as the electrophile (instead of the nitro group, which would be
nitration).2 This reaction is used in the synthesis of aspirin. The Kolbe reaction creates
salicylic acid when sodium phenoxide attacks a carbon dioxide molecule, then undergoes
tautomerization to form sodium salicylate, which is then protonated to form the salicylic
acid. The salicylic acid is then reacted with acetic anhydride to synthesize acetylsalicylic
acid, or aspirin. Aspirin is a high selling commercial drug that utilizes electrophilic
aromatic substitution reactions, and various other forms of substitution reactions are used for
a variety of syntheses.
Methodology:
The mixture was cooled to 0C prior to the addition of 8 mL of an equal volume mixture of
sulfuric and nitric acids. The reaction mixture was warmed to room temperature and reacted
for 15 minutes.
The reaction was stopped when poured over 50g of crushed ice which also
precipitated our product. Crystals were isolated using vacuum filtration with a Büchner
Funnel. The crystals were washed twice with 25 mL cold water followed by two washes
with 10 mL ice cold methanol. The dry product was weighed for recovery.
Three grams of acetanilide was mixed with 5 mL of concentrated sulfuric acid. The
acetanilide was dissolved swirling and stirring the mixture. After the flask was cooled in an
ice bath, a mixture consisting 1.8 mL of concentrated nitric acid and 5 mL of concentrated
sulfuric acid was added dropwise using a disposable pipet. The reaction was cooled after
After 20 minutes, including the time required for adding the nitric-sulfuric acid
heated. The dilute sulfuric acid already present in the flask served as the hydrolyzing
medium. Heating the mixture allows the solids to dissolve. The flask was cooled in an ice
bath and 30 mL of concentrated aqueous ammonium hydroxide was added. The nitroaniline
isomers precipitated during this step. The precipitated nitroaniline was collected using a
Büchner funnel. The solid was washed with small amounts of water (total about 50 mL).
The dry material was added to hot ethanol and dissolved. After boiling, when the
first crystals appeared, the flask was placed in an ice bath to complete the crystallizaiton.
Crystals of p-nitroaniline were collect by vacuum filtration. The crystals were wash with a
minimum amount of cold ethanol and allowed to dry. Crude p-nitroaniline was dissolved in
15 mL ethanol for each gram of p-nitroaniline and the solution warmed to dissolve the solid.
About 0.5g of activated charcoal was added to the solution and swirled for a few minutes.
The charcoal was removed by gravity filtration. The filtrate was concentrated to about 1/3 of
its original volume by heating on a hot plate. When the solution cooled, and the first crystals
appeared, the flask was placed in an ice bath. After the crystals were collected, they were
mL round bottom flask. After adding all the dichloromethane, the flask was stoppered.The
cooled suspension of aluminum chloride and methylene chloride was stirred using a stirring
bar. 1.6g of acetyl chloride, along with 4 mL of dichloromethane, was added to the reaction
apparatus over a 15 minute period. After addition was complete, 1.4g of toluene was
minutes. After this addition, reaction was allowed to proceed for 30 minutes, swirling
frequently.
The reaction mixture was poured into a mixture of 10g of ice and 5 mL of
concentrated hydrochloric. This solution was mixed thoroughly for 10 to 15 minutes. Using
a separatory funnel, the organic layer was collected and saved. The aqueous layer was
extracted with 6 mL of dichloromethane. The two organic layers were combined. The
organic layers were washed with 10 mL of saturated sodium bicarbonate solution and then
to form Methyl-m-nitrobenzoate, where a nitro (NO2) group was added to the methyl
The Methyl Benzoate (1) was first mixed with concentrated sulfuric acid (2), then a
mixture of concentrated sulfuric acid and concentrated nitric acid (3) was added.1 The
sulfuric acid /nitric acid mixture was necessary to form the nitronium ion from the nitric
acid. Nitric acid isn’t a strong enough electrophile to react with the aromatic benzene ring,
but the nitronium ion with the positive charge on the nitrogen is a strong electrophile and
The addition of the nitric/sulfuric acid mixture was added drop-wise over a period of
15 minutes to reduce the amount of by-product that could be formed in the reaction. The
addition of the mixture allowed the nucelophile (methyl benzoate) to attack the electrophilic
nitronium ion forming the arenium carbocation intermediate. Then the conjugate base from
the deprotonation of the sulfuric acid (HSO4-), removes a proton from the meta-intermediate
to reform the aromatic ring structure, and yielding the final product, Methyl-m-
nitrobenzoate.
Once the acid was added, the mixture was cooled without stirring, then added to
crushed ice to stop the reaction. The crude product was isolated via vacuum filtration, then
impurities were removed using hot methanol and centrifugation. The percent yield of the
experiment was 26%, and calculations are shown at the end of the paragraph. The melting
point of the final product was 76.6°C-78.9°C, which compared to the literature value (78°C)
was close enough to suggest a successful addition of the nitro group.1 The IR spectra also
shows the characteristic aromatic ring stretches (3092.51, 1500-700, and 670), and at
1525.84 the nitro group stretch which indicates that the experiment was successful in adding
the positive charge at either the ortho, para, or meta position. The major product is the meta
product due to the carboxyl and nitro groups both being powerful electron withdrawing
groups. The meta attack on the methyl benzoate is the only attack that doesn’t yield have a
resonance structure that isn’t highly unstable, so the meta attack is the most resonance
While the percent yield was a little low for the experiment, the melting point data
and the IR spectra both support the notion that the nitro group was successfully added to the
methyl benzoate. Additional reading on the subject allowed for the defense of the meta
attack as opposed to the ortho or para attack of the nitro group, which was a successful
learning opportunity to see “nature’s laziness”, or the desire to form the structure with the
Experimental Section:
All chemicals used in this experiment were provided by the PLU stockroom, and the
infrared spectrometer, the melting point apparatus, and the centrifuge machine in the open
lab were also used. A vacuum filtration system was also assembled and used to isolate the
product.
Methyl-m-nitrobenzoate- From the lab manual, the procedure was followed and .210
(.0016 mol) methyl benzoate was added to a tared 3-ml conical vial, and then weighed to
determine the actual weight of the methyl benzoate.1 .45 ml (.008 mol) concentrated sulfuric
acid was added to the vial and the vial was then attached to an air condenser (to help hold
the vial in place). The vial and air condenser were then submersed in a 250-ml beaker ice-
bath. A chilled mixture of .15 ml (.0033 mol) concentrated nitric acid and .15 ml (.002 mol)
sulfuric acid was added drop wise via a Pasteur pipette over a period of 15 minutes, through
the air condenser into the vial. Once the acid was added, the reaction mixture was allowed to
acclimate to room temperature in a 250-ml beaker with a water bath at room temperature for
15 minutes unstirred. After the mixture had sat, it was transferred via Pasteur pipette into a
20-ml beaker containing 2.0g crushed ice. The ice was allowed to melt and then the mixture
(white and chunky consistency) was vacuum filtered using a Hirsch funnel wand washed
with two 1-ml portions of cold water and two 0.3-ml portions of ice cold methanol. Once
dried, the crude product was weighed and then added to a Craig tube for recrystallization.
For recrystallization, methanol was boiled using an Erlenmeyer flask on a hot plate
and then 4 drops of methanol was used to dissolve the crude product in the Craig tube. After
being dissolved, the mixture sat at room temperature for approximately 5 minutes and then
was submersed in an ice-water bath for another 5 minutes for crystallization to occur. The
Craig tube was then placed in the centrifuge machine to isolate the crystals from the mother
liquor. The final product, Methyl-m-nitrobenzoate, was weighed using a watch glass, percent
yield was calculated, melting point measured, and an infrared reading was taken.
Infrared Spectra Frequencies: 3092.51, C-H aromatic stretch; 2961.21, CH3 (C-H)
References:
1) Engel, R.G.; Kriz, G.S.; Lampman, G.M.; Pavia, D.L. (1999). Introduction to
Eighth Edition. Hoboken, New Jersey: John Wiley & Sons Inc.
References:
1) Engel, R.G.; Kriz, G.S.; Lampman, G.M.; Pavia, D.L. Introduction to