03/28/2024

Diels-Alder Reaction
Dr. Galina Melman
Ledina Banushllari

Introduction:
Diels-Alder Reaction is a method in organic synthesis that is used to successfully form
six-membered rings by having good control over the regio and stereochemical outcomes.
Rings are produced by cyclization of non-cyclic compounds with a single carbon-carbon
bond and simultaneous construction of two new carbon-carbon bonds. Reacting 1,3-diene
with an alkene is one of the most used ways to get a derivative of cyclohexane In this case,
the alkene is the dienophile. The Diels-Alder reactions are free of several side reactions and
often give high yield of the product.

From researchgate.net

Reactants react with each other and a six-membered transition state is formed
During the transition state, reorganization of pi electrons occur, three pi bonds break, two
sigma bonds and 1 pi bond are formed simultaneously. Orbital symmetry controls the
pericyclic reaction while little charge or free-radicals are developed at the carbon atoms. The
diene adapts to a planar conformation with a 0 degree angle between the two double bonds.
To favor Diels-Alder reaction, the diene must be conjugated and in s-cis conformation. If this
cisoid conformation is not achieved, the Diels-Alder reaction will happen very slowly or not
at all. The reaction is bimolecular and shows high stereoselectivity and is specific to the
substrate used. Dienophile can be an alkene or a compound that contains double bonds.
The more withdrawing groups a dienophile has the more reactive it is and the faster the
reaction can happen.

Materials and methods:

Refer to the attached pages.

Observations:
When sulfolene and maleic anhydride are dissolved in xylene the compound becomes a
cloudy solution and when reflux is performed, a drying tube is put on top of the condenser to
exclude moisture from the atmosphere. The SO2 gas formed through the condenser was
visible and looked like smoke.
Mass of the crystals obtained was 1.53 g and the melting temperature range was 75- 80 C.
The crystals had a brownish color because not enough petroleum ether was added.
Discussion:

Maleic anhydride shows very good dienophile properties because of the two electron
withdrawing groups, carbonyls. These groups cause the two carbons that form the alkene to
be more disposable to get attacked by the pi electrons of the diene.
1,3-butadiene is a product of decomposing 3-sulfolene by heating it up. This decomposition
also creates SO2 gas which can be irritant and dangerous. The diene formation is a reverse
Diels-Alder mechanism because two carbon-sulfur bonds are broken. Working with
concentrated solutions of the two alkenes is important in order to get a thermodynamically
stable and energetically favored product. If the reagents were not concentrated then the
cycloaddition would not occur. Since the reaction is bimolecular the rate depends on the
concentrations of the reagents. The higher the concentration the faster the rate.
Sulfolene was taken in excess in order to obtain the diene. If sulfolene was not taken in
excess, the decomposition would not be able to occur, hence the cycloaddition would be
impossible as well.
Nonpolar xylene is used for this reaction because it shows a similar structure to the transition
state which is an important factor because it also stabilizes the transition state. Also, Diels
Alder reactions require high heating to occur so xylene has a high boiling point and allows
the reaction to be heated to high temperatures. At high temperatures and if xylene was wet,
moisture could hydrolyze maleic anhydride to carboxylic acid so a drying agent is required
such as calcium chloride.
For purification petroleum ether was added to the hot solution until the solution turns cloudy
and vacuum filtration is performed to separate the crystals. Petroleum ether washes the
product isolated and because it is a poor solvent, it does not react with maleic anhydride so
it will not dissolve it. Mixed solvent recrystallization method was used which were xylene and
petroleum ether.
The accepted melting point of pure 4-cyclohexene-cis-1,2-dicarboxylic anhydride is 97-103 C
while the melting point of the product obtained was 75-80 C. One reason could be starting
the refluxing timer before the first drop (earlier) and accidentally having the temperature go
above 65 C during reflux. Another reason could be fast addition of 10 mL xylene which may
not allow time for cycloaddition. Some of the xylene may have been sticking on the
condenser’s wall instead of reaching the solution. The last reason could be not adding
enough petroleum ether which caused brown colored crystals instead of white crystals,
which might have lowered the melting point.
Conclusions:
Diels Alder reactions allow simultaneous increase in the number of rings, asymmetric
centers and functional groups. They are widely used in chemical transformation in organic
synthesis used for pharmaceuticals, materials etc. The reaction is highly selective and
tolerable of a variety of functional groups such as carbonyl, hydroxyl, amines, alkenes etc.
Overall, Diels Alder reaction is a necessary tool to construct complex organic cyclic
molecules.