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The Semi-Microscale Diels-Alder Reaction

of Anthracene with Maleic Acid
Instructor : Dilusha Harischandra ,PhD

Student: Betty Weiss

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Lab SYNT 717: The Diels Alder Reaction of Anthracene with Maleic Anhydride.
Semi-Microscale Diels Alder Reaction
by : Betty Weiss
Date of experiment:
February 29, 2016

INTRODUCTION
In 1950 Otto Diels and Kurt Alder have been awarded the Nobel Prize for Chemistry. They described a
very important reaction, which is suitable for the formation of carbon-carbon bond in a six membered
ring with high stereo chemical control.

Otto Diels

Kurt Alder

1876-1954

1902-1958

Since1928severalnewcompoundshavebeensynthesizedwiththeuseofDielsAlder(DA)reaction.
Thisreactionprovidesaneasierwayforcyclizationthanotherringclosureproceduresofopenchain
compounds.

OBJECTIVE
The purpose of this experiment is to form 9, 10-dihydroanthracene-9,10-, -succinic anhydride by

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way of a Diels Alder reaction between anthracene and maleic anhydride. Anthracene acts as the diene
and maleic anhydride functions as the dienophile. Following the reaction, the crude product will be
recrystallized. Melting points of both the crude product and recrystallized product will be taken and
compared with the literature value. Also, an infrared spectrum of the recrystallized product will be
taken. Both melting points and the infrared spectrum will be used to characterize the product.

CHEMICAL REACTION

C14H10 + C4H2O3 C18H12O3

MECHANISM

Figure 1: Antracene s ring reacts as a diene, the product has two fully aromatic rings, each with six pi
electrons.
MATERIALS
250 ml beaker
boiling chip
Buchner funnel, with adapter
condenser with tubing, electric flask heater, hot plate, support stand
50 ml Erlenmeyer flask
125 ml filter flask with vacuum tubing, filter paper
10 ml graduated cylinder
25 ml round bottom flask
13x100 mm test tube
2 melting point capillary tubes
micro spatula
watch glass
3 ml product vial

REAGENTS AND PROPERTIES

1.

Anthracene 98 %
C14H10
MM: 178.23 g/mol
MP: 216-218 C
BP: 339.9 C
Hazard: Unlike many other polycyclic aromatic hydrocarbons (PAH), anthracene is not classified as
carcinogenic as listed by the U.S. agency OSHA. Anthracene, as many other PAHs, is generated during
combustion processes: Exposure to humans happens mainly through tobacco smoke and ingestion of
food contaminated with combustion products. Irritant.
2.

Maleic Anhydride
C4H2O3
MM: 98.06 g/mol
MP: 54-56 C
BP: 202 C

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Hazard: This compound also poses relatively low-risk environmental hazards, an important feature for
those applications. Exposure to maleic anhydride may cause respiratory tract, eye irritation, skin
irritation and respiratory irritation. Maleic anhydride is a skin and respiratory sensitizer. Toxic and
corrosive.
3.

Potassium Bromide
KBr
Hazard: Potassium bromide KBr is a salt widely used as an antiepileptic drugs and a sedative in the
late 19th and early 20th centuries, with over-the-counter use extending to 1975 in the US. Its action is
due to the bromide ion, KBr is equally effective. Potassium bromide is used as a veterinary drug, as an
antiepileptic medication for dogs.
Under standard conditions, potassium bromide is a white crystalline powder. It is freely soluble in
water. In a dilute aqueous solution, potassium bromide tastes sweet, at higher concentrations it tastes
bitter, and tastes salty when the concentration is even higher. These effects are mainly due to the

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properties of the potassium ionsodium bromide tastes salty at any concentration. In high
concentration, potassium bromide strongly irritates the gastric mucous membrane, causing nausea and
sometimes vomiting. Irritant and hydroscopic.
4.

Xylene (1,2 dimethylbenzene)

C8H10
MM: 106.17 g/mol
MP: - 47.4 C
BP: 138.5 C (137-144 C)
Hazard: Xylene is an aromatic hydrocarbon known for its wide usage in tissue processing, staining and
cover slipping in the histology laboratory. Exposure to xylene can occur via inhalation, ingestion, eye
or skin contact. It is primarily metabolized in the liver by oxidation of a methyl group and conjugation
with glycine to yield methyl hippuric acid, which is excreted in the urine. Smaller amounts are
eliminated unchanged in the exhaled air. There is a low potential for accumulation. Xylene causes
health effects from both acute (<14 days) and also chronic (>365 days) exposure. The type and severity
of health effects depends on several factors, including the amount of chemical you are exposed to and
the length of time you are exposed for. Individuals also react differently to different levels of exposure.
Flammable and irritant.

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5.

9,10-dihydroanthracene9,10-,-succinic anhydride
(product)
C18H12O3
MM: 276.29g/mol
MP: 262-264 C
Hazard: Harmful if swallowed, causes skin, eye irritation and respiratory irritation.

PROCEDURE
Part 1 Reacting Anthracene with Maleic AnhydrideTare a 25-mL roundbottom flask and record the
mass. Weigh 0.5 g of anthracene and 0.25g of maleic anhydride and place them in the 25 ml round
bottom flask. Add 6.0 mL of xylene and a boiling chip. Fit the vial or tube with a condenser, as shown
in Figure 2 on Chemistry Lab Experiments SYNT 717. Turn on the water to the condenser and heat the
mixture , use a 200C sand bath to heat the mixture at reflux for 30 minutes, boiling vigorously to
ensure good mixing. Cool the mixture to room temperature and prepare an ice bath using a 250-mL
beaker. Then cool the mixture in the ice bath for approximately 5 minutes. At the same time, pour 6 mL
of xylene into a test tube and chill the xylene in the ice bath. Collect the recrystallized solid by vacuum
filtration using a Buchner funnel and rinse the crystals with 3 mL of ice-cold xylene. Weigh the crude

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product and set aside a small sample to dry. This sample will later be used to measure the melting point
of the crude product.

Figure 2: Refluxing apparatus with condenser

Figure 3: Bchner flask with funnel

Part 2 Purifying the ProductTo perform recrystallization; place the product in a 50-mL Erlenmeyer
flask. Add 5-10 mL of xylene and heat the mixture gently in a sand bath until the xylene boils.

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Gradually add more xylene until the entire product dissolves or until no more appears to be dissolving.
Be sure not to exceed 15 mL of total volume xylene. If solid impurities are still present, use a Pasteur
pipet to transfer the solution to another 10-mL Erlenmeyer flask. Allow the solution to cool to room
temperature and then cool the solution in an ice bath for 5 minutes. If its necessary, scratch the bottom
of the flask with a glass rod to induce crystallization. Collect the crystallized solid by vacuum
filtration, using a Buchner funnel and rinse the crystals with 3 mL of ice-cold xylene. Spread the
product crystals thinly over a clean watch glass and allow them to dry for approximately 30 minutes.
Then weigh the product and record the mass, than place the product in a labeled vial.
Part 3 Characterizing the ProductMeasure the melting points for both the crude product and the
recrystallized product. Perform an infrared spectrum on both products. Add 100 mg KBR to
approximately 1 mg of the product. Mix the two using a mortar and pestle, being sure to grind the two
compounds into a fine powder. Place some of this mixture in a microcup, making sure the surface is
smooth. Then place the pellet in the infrared spectrometer and obtain an infrared spectrum of the
product. Compare the product spectrum with the spectra of maleic anhydride and anthracene in order
to characterize the product.
Part 4 Clean-upplace,all materials in their appropriate waste containers, and wash your glassware
with a soap detergent.
RESULTS AND CONCLUSIONS
Empty 25 ml round-bottom flask: 26.083g
Antracene : 0.5521 g
Maleic anhydride: 0.2682 g
Weight of the Crude product: 1.2834 g
Weight of empty watch glass: 57.3508 g

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Weight of watch glass and product: 57.6507g
Final weight of 9,10-,-succinic acid anhydride : 0.2999 g
Appearance: white, slightly gray in color, bright crystals
Crude Melting Point: 255-264.4 C
Measured Melting Point: 262-265 C

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Theoretical yield of the product 0.776 g

Wavenumber(cm1)andTransmittance(T%)

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3083
2985
2926
1863
1782

87
84
85
39
8

1643
1443
1416
1226
1069

74
77
67
44
36

Figure 4: Displaying IR spectrum of the product.

REFERENCES
http://www.physicspost.com/science-article-74.htlm

1010
913
828
722
662

35
25
88
67
67

568

82

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POST-LABORATORY QUESTION : SYNT 717 (BETTY WEISS)

1. The percent yield for the crude product was 77.05 %. The percent yield for the recrystallized product
was 47.42%.
2. The percent recovery from recrystallization was 54.21%.
The Diels-Alder Reaction of Anthracene with Maleic Anhydride
3. Hydrolysis of the Product: The carbons, which are attached to the oxygen molecules by a double
bond, carry a slightly positive charge. Since oxygen is more electronegative than carbon, it pulls the
electrons towards it and carbon is left with a slight positive charge. A water molecule with a lone pair
of electrons on the oxygen attacks the slightly positive carbon atoms. The water attaches, and then
loses a proton in order to stabilize the positive charge. Thus, two hydroxide groups are added to the
molecule. The mechanism of the reaction and the product of this hydrolysis reaction are both shown
above.

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4. Recrystallizing an anhydride such as the product from this experiment from water or from an
alcohol is rarely a good idea. This is because anhydrides react with water in the air and form a new
product. When water or alcohol is around, the lone pair of electrons on the oxygen react with the
product and the product undergoes a hydrolysis reaction to form a different product, as shown above in
question 3. Thus, the recrystallized product would not be the same product obtained in the Diels Alder
reaction between anthracene and maleic anhydride. The product (9, 10- dihydroanthracene-9,10-, succinic anhydride) in the reaction that was performed in this experiment reacts slowly and is easily
isolated and characterized before hydrolysis can occur.

5. (a) The carbonyl region of the product IR spectrum yielded peaks at 1863 cm
the maleic anhydride spectrum, the carbonyl peaks were located at 1850 cm

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and 1782 cm . On

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and 1778 cm . These

are relatively close, and indicate that both the product and the maleic anhydride have carbonyl groups
that together have aldehyde functionality.
5. (b) Yes, the product IR spectrum allows me to confirm that the structure of the product is a
combination of the reactants anthracene and maleic anhydride. The product spectrum yields peaks at
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3083 cm and 2985 cm . These indicated the presence of two benzene rings, and were comparable to
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peaks at 3055 cm , 2988 cm , and 3009 cm on the anthracene spectrum. The product IR spectrum
also contained peaks at 1863 cm

-1

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and 1782 cm . These peaks indicated the presence of carbonyl

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groups, and were comparable to peaks located at 1856,1848 cm and 1783 cm on the maleic
anhydride spectrum. Because the product spectrum shares similarities with both the maleic anhydride
spectrum and the anthracene spectrum, it can be concluded that the product is a combination of the two
reactants.

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Figure 5: Displaying spectrum of anthracene

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Figure 6 : Displaying spectrum of maleic anhydride

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Figure 7: Displaying NMR spectrum of 9,10- dihydroanthracene- 9,10 ,-succinic anhydride