Lead Author: Clara Wan

Reviewer: Lakshmi
Editor: Josh Purvis
Diels-Alder Reaction Using Anthracene and Maleic Acid
Introduction
Reactions that form rings are very useful synthetic tools in organic
chemistry, and the most common reaction to form unsaturated sixmembered rings is the Diels-Alder reaction1. This reaction occurs between a
conjugated diene (in an s-cis conformation) and a dienophile, and is driven
by the formation of 2 sigma-bonds, which are energetically more favorable
than the pi-bonds. In order for the sigma-bonds to form, the molecular
orbitals of the two molecules must overlap. Specifically, the highest-occupied
molecular orbital (HOMO) of the diene must overlap with the lowest
unoccupied molecular orbital (LUMO) of the dienophile. Electron-withdrawing
groups on the dienophile increase the rate of reaction as these groups lower
the energy of the LUMO2.
Figure 1: Mechanism of Diels-Alder formation from Anthracene and Maleic
Anhydride
O
O

Figure 1 shows the formation of the Diels-Alder adduct from Antracene and
Maleic Anhydride
Table 1 Table of Reagents
Name
Molecular
Weight
(g/mol)
Xylene
106.2
Anthracene 178.2
Maleic
98.06
Anhydride
Adduct
276.3
CaCl2
111.0

Melting
Point (oC)

Boiling
Point (oC)

Density
(g/mL)

13.20
217.0
55.00

138.4
340.0
202.0

0.861
1.250
1.480

261.5
772.0

1935

2.150

H2O
18.00
0.000
100.0
1.000
Table 1 shows a list of material used in the experiment and some applicable
properties of each.
Experimental
To begin, 0.3g anthracene and 0.15g maleic anhydride were added to a
10mL round-bottom flask. Next, 6 mL of xylene and a spin bar were added to
the flask before attaching a reflux condenser. The reaction flask was heated
using a sand bath which was situated on top of a hot plate for 30 minutes.
The hot plate was not used to heat, only to stir the mixture. After 30 minutes,
the flask was allowed to cool to room temperature before being placed in an
ice bath for 10 minutes. The Diels-Alder adduct was then collected using
vacuum filtration. In order to remove the crystals from the reaction flask, the
mixture was washed with 1.5mL icy xylene. The solid was placed in the oven
for 10 minutes to allow it to dry, and finally the mass and percent yield were
calculated.
Results
After the product was dried appropriately, the melting point was
determined to be___ and the mass of the product was determined to be 0.1g.
In order to determine the efficacy of the experiment the percent yield was
determined. The reaction occurs at a 1:1 ratio and Maleic Anhydride serves
as the limiting reagent. The theoretical yield was first determined using the
limiting reagent, Maleic Anhydride, and was found to be 0.42g. This was then
used to find the percent yield, which was 23.8%.
Equation 1:
Theoretical Yield=0.15 g Maleic Acid

1 mol Maleic Acid

1 mol Adduct
176.29 g Adduct

=0.42 g
98.06 g
1 mol Maleic Acid
1 mol Adduct

Equation 2:
ActualYield
0.1 g
=
=23.8
|Theoretical
|
Yield 0.42 g

Percent Yield=

Discussion
In this experiment, the Diels-Alder product looked like a powdery, white
substance and the percent yield was determined to be 23.8% which is not a
very high yield. The yield could have been increased by refluxing for a longer
period of time to ensure more of the reactants reacted. A lot of product was
also stuck to the side of the round bottom flask and flushing the flask with

xylene did not force the product out of the flask. This could have been fixed
by using a larger round bottom flask so that an apparatus could be inserted
into the flask and used to scrape product off of the side.
Conclusion
There was not much Diels-Alder product, however the product that was
achieved was relatively pure, as seen by the melting point. The melting point
was a little lower than the expected temperature, showing how the product
did probably contain some impurities. Most likely, the impurity was water
because some of the product was not able to be dried in the oven without
burning some of the other product.
References
1. Barbaro, John; Hill, Richard. Experiments in Organic Chemistry, 3rd
Edition; Contemporary Publishing Co. of Raleigh, Inc., 2005.
2. Diels-Alder Reaction. Organic Chemistry Portal. http://www.organicchemistry.org/namedreactions/diels-alder-reaction.shtm (accessed 31
March 2016)