CH 227

The Diels Alder Reaction (adapted from Organic Chemistry: A Short Course,
H. Hart, L. E. Craine, D. J. Hart, and T.K. Vinod 13th ed. Houghton-Mifflin, Boston,
2012.)

One of the most useful methods for constructing six-membered rings is the
cycloaddition of an alkene to a conjugated diene. The simplest example is the addition of
ethylene (called the dienophile) to a 1,3-butadiene (the diene) to give cyclohexene:

‡
CH2 CH CH2
CH CH2 CH CH CH CH2
+
CH CH2 CH CH2 CH CH2
CH2 CH2 CH2

Because the carbon atoms of the double bond in the dienophile add to the ends of the
conjugated diene system, the reaction is described as a 1,4-cycloaddition reaction. It is
also called the Diels-Alder reaction, after Otto Diels and Kurt Alder, who shared the
1950 Nobel Prize in chemistry for its discovery.

1
2 CH2 CH2
CH CH2 CH CH2
CH CH2 CH CH2
3 CH2 CH2
4

The transition state for this reaction resembles an aromatic system because it involves
six π electrons. The double bonds in the diene component must be in a cisoid
conformation to attain the geometry of the transition state. For this reason, the reaction
proceeds best with cyclic dienes, such as cyclopentadiene, in which the double bonds are
fixed in a cisoid conformation by being part of the ring.

CH2 CH2
CH CH
CH CH
H2C CH2

transoid required cisoid cyclopentadiene;

arrangement the double bonds
are fixed in the cisoid arrangement

Most Diels-Alder reactions are reversible. The reverse process, called a retro-Diels-
Alder reaction, is favored at higher temperatures.
 Preparation of a Butadiene Adduct from 3-Sulfolene

In this experiment, 3-sulfolene will be heated in the presence of the dienophile maleic anhydride.

SO2 heat + SO2

1,3-butadiene

The released butadiene from the retro Diels-Alder reaction will react with the dienophile
to form an adduct, cis-4-cyclohexene-1,2-dicarboxylic anhydride.

O H O

O
heat O
+
H O
O

CAUTION
1. All the glassware must be dry.
2. The reaction is exothermic. Do not overheat.
3. 3-Sulfolene is irritating to the skin and eyes, and maleic anhydride is a respiratory hazard. Avoid
skin contact and do not inhale the dust of either substance.
4. Sulfur dioxide is generated in the reaction; adequate ventilation is necessary.
5. Petroleum ether, xylenes, and toluene are flammable. Do not let them come into contact with the
hot surface of your hot plate/stirrer.

Combine 2.0 g of 3-sulfolene, 1.2 g of finely powdered maleic anhydride, 1.0 mL of xylenes and
a magnetic stir bar in a 25-mL round-bottomed flask. After this addition, stopper the flask with
the glass stopper to avoid moisture. Remove the glass stopper and fit the flask with a water-
cooled reflux condenser carrying a calcium chloride drying tube on top (Figure 1).

Drying
Tube
with CaCl2
Thermometer
Adapter

Water Out to Sink

Clamp to Water in from Sink

Bar in Hood
Reaction Flask

Magnetic
Stir Bar

Sand Bath
(Metal Dish)
Hot Plate/Stirrer

Lab Jack

Figure 1. Reflux Apparatus with Drying Tube

 Turn on the magnetic stirrer and begin heating the mixture gently. All the solids should
melt/dissolve. Maintain the rate of heating to sustain a gentle reflux (boiling liquid
condensing and dripping back into the flask) for 30 min. Overheating and strong reflux is
not recommended, this will cause the reaction mixture to become brown. If this happens,
start over.

During the reflux time you will probably see the generation of white smoke, SO2.

After the reflux period, lower the hot plate and allow the flask to cool for 5 min. If the
contents become too cool, the product will form a hard cake that is difficult to redissolve.
Remove the condenser and add 5 mL of toluene and a tip of a spatula of activated
charcoal to the flask. Activated charcoal helps to remove the impurities that produce the
dark color in solution. The charcoal does not dissolve.

Reattach the condenser with drying tube and bring the suspension to a boil using the hot
plate/sand bath. You should not have any solid at this point. If you have solid, add
another 2-3 mL of toluene and reheat to dissolve. Carefully disassemble the reflux set up,
and filter the hot solution quickly through a fluted filter paper into a dry 125 mL
Erlenmeyer flask. Right after the filtration you should see the formation of a white solid.
If this happens, place the flask in an ice-water bath to maximize crystallization of the
product. Use a Bűchner funnel to collect the product by vacuum filtration. Rinse the
crystals with two portions of about 5 mL of cooled petroleum ether.

Spread the product on a sheet of filter paper. Let it dry until next lab period. Once dried,
weigh it, calculate the yield and take its melting point. The purified product is a white
powder with melting point 103-104 ˚C. The name of your product is cis-4-cyclohexene-
1,2-dicarboxylic anhydride.

When you have completed analysis of your compound, place it into a vial labeled with
your section number, group member names (first names are OK), and “Diels-Alder
Product.” Use your Sharpie© pen in your drawer to label the vial. Turn it into the
stockroom.

CLEANUP
All liquid wastes go into the liquid organic waste containers in the hood.