Organic Chemistry 2
NCHM62310
Report
Experiment 1: Diels Alder Reaction (reaction of 1,3-butadiene and maleic anhydride)
Surname and initials: Ramiah S
Student number: 202220501
Date: 11 March 2024
Introduction
Diels-Alder reaction is a cycloaddition reaction between a conjugated diene (two double bonds
separated by a single bond), and a compound containing a C-C double bond- dienophile- to form an
unsaturated six membered ring. Furthermore, reactions involving conjugated dienes produces two
products, 1,2 and 1,4 addition products. With every reaction, there are certain limitations: the dienophile
must have at least one 𝜋 bond and an electron withdrawing group. The diene must strictly be conjugated
and in an s-cis conformation (s-cis is when the double bonds are cis in reference to the single bond) as the
molecules’ terminal p-orbital cannot react if they are not overlapping correctly in order for the Diels-
Alder reaction to occur.
The objective of this experiment was to demonstrate the cycloaddition reaction, which produces six-
membered rings. Thus a 1,3-diene and an alkene reacted in a cycloaddition reaction in the presence of
xylene to form a six-membered ring. Consequently, the product, 4-cyclohexene-cis-1,2-dicarboxylic
anhydride, was formed during this reaction between 1,3-butadiene (diene) and maleic
anhydride(dienophile)- Figure 1. However, only the 1,3-butadiene cis- conformation will experience
cycloaddition; the trans- conformation will not. In this experiment, as depicted in the main reaction in
Figure 2 below, 3-sulfolene's thermal decomposition served entirely to produce the cis- conformation.
The electron-rich diene that is formed, interacts with the electron-poor maleic anhydride. The Diels-Alder
anhydride produced was then hydrolysed to produce the carboxylic acid.
Main Reaction and Mechanism:
O O
H
O O
H
O O
Figure 1: The main reaction above is 1,3-butadiene with the addition of maleic anhydride. The solvent is
xylene. The product is 4-cyclo-cis-1,2-dicarboxylic anhydride.
Figure 2: In part 1 of the experiment, 3-sulfolene was thermally decomposed to synthesize 1,3-butadiene.
Lastly, the dienophile, maleic anhydride, attacks the diene, forming 4-cyclohexene-cis-dicarboxylic acid.
General mechanism of Diels-Alder Reaction between 1,3-butadiene and maleic anhydride
Experimental Procedure
In a 25 mL round bottom flask equipped with a magnetic stir bar, 3-sulfolene (2.5008 g), maleic
anhydride (1.5095 g), and 1.0 mL of dry xylene were dissolved. The setup was then assembled with a
reflux apparatus, including a gas trap. The reaction was allowed to heat up using a sand bath, to which it
was refluxed after 30 minutes. An additional 10 ml of xylene was added and then heated for a minute
until all the precipitate was dissolved. Upon observation, the resulting mixture displayed a brown colour.
The solution was transferred to an Erlenmeyer flask. Since the solution did not crystallise during the
transfer, there was no need for reheating. Upon precipitation, petroleum ether (10 mL) was added to the
solution until it turned cloudy. A compound of 4-cyclohexene-cis-1,2-dicarboxylic anhydride was
obtained through filtration using a filter paper and was then transferred to a watch glass for air drying.
The mass of the collected crystals was 1.6475 g.
Results and Discussion
Table of reactants:
Compound Molar Weight Mass obtained Moles Properties
Theoretical
3-sulfolene 118.15 g/mol 2.5008 grams 0.0211 mol MP = 64 - 650C
Maleic anhydride 98.06 g/mol 1.5576 grams 0.0159 mol MP = 52.8 - 600C
Xylene 318.50 g/mol 1 mL used as NA Flammable
solvent liquid
Figure 4: Table depicting the reagents used during the reaction.
Table of Products:
Compound Molar Weight Theoretical yield Theoretical Properties
4-cyclohexene-cis1,2- 152.16 g/mol 2,4168 g Hydrophilic, MP =
dicarboxylic anhydride 103 – 1040C
(According to Lab
Manual, Dailey p. 28)
Figure 5: Table depicting the product formed upon completion of the reaction.
Stoichiometric Calculations:
i. Calculating the limiting reagent:
2,5008 g
n (C 4 H 6O 2 S)= =0,0211
g mols
118 ,5
mol
1,5576 g
n ( C 4 H 2 O3 ) = =0,0159
98 ,06 g mols
mol
Therefore, the limiting reagent will be maleic anhydride.
ii. Calculating the theoretical yield:
1,5576 C4 H 2 O3 152,149 C8 H 8 O3
× =2,4168 g of C 8 H 8 O3
g 1 mol
98 , 06
mol
Theoretical Yield:
1,6475 g
×100=68 ,12 %
2,4168 g
The actual yield of the 1,3-butadiene and maleic anhydride Diels-Alder process was found to be 1.6475g,
whereas the theoretical yield was calculated to be 2.4168g. This translates to 68.12% of the theoretical
yield as the overall percentage yield. The discrepancy in this experiment's theoretical and actual yields
could have been caused by various variables. Losses incurred during the purification and separation
processes could be one of the causes.
Results may also vary depending on the compounds' melting and boiling temperatures. For successful
purification, the solvent employed in recrystallization should have a boiling point that is much higher than
the product's melting point. An incomplete reaction is another possible reason for the reduced yield. This
might be resolved by keeping a closer eye on the reaction, making sure the reaction mixture is well-
stirred, and giving the reaction enough time to finish. To further speed up the process and raise the yield
overall, a catalyst like a Lewis acid may be employed. The reaction's outcome may also be impacted by
the solvent selected. In this experiment, the solvents xylene and petroleum ether were utilised. The
boiling point of xylene is approximately 140°C, while that of petroleum ether is approximately 40–60°C.
This difference in temperature can have an impact on the yield and rate of reaction. Using xylene, which
has a higher boiling point than other substances, could result in a more effective reaction since it raises
the temperature of the reaction mixture, which could increase the yield and rate of the reaction. But using
a solvent with a high boiling point may also cause more volatile molecules to be lost, including 1,3-
butadiene, which could have a detrimental effect on the yield.
One possible source of the contamination is the drying process. The anhydride was in contact with air
during the drying process. It is possible that the extremely hydrophilic anhydride in the air reacted with
moisture to change the molecule into its dicarboxylic acid state.
Since the anhydride has a far lower melting point than dicarboxylic acid, the unknown impurity in the
first product must have a melting point that is lower than 100°C. The other option is either maleic
anhydride or the unreacted 3-sulfolene, which have a lower melting point than the anhydride product.
Some of the product from the filter paper could have been lost. When this product is dried and weighed,
the value for the actual yield will be lower than expected because of this loss of product. Anhydride
product of Diels-Alder reaction could have possibly hydrated before extraction, causing it to be soluble in
petroleum ether. And lastly, the 1,3-butadiene could have evaporated before it had a chance to react with
the maleic anhydride.
Instead of crystallising out of the solution, as would have happened with the intended result, any
unreacted maleic anhydride or 3-sulfolene should have dissolved in the water during the hydration phase.
Due to its strong polarisation at the oxygen-containing end, the dicarboxylic acid that is still dissolved in
the solution may have contributed to the reaction's product loss.
Conclusion
This reaction succeeded in its goal of illuminating the cycloaddition reaction, which yields rings with six
members. It was found that the cis-isomer of 1,3-butadiene was produced by the thermal breakdown of 3-
sulfolene (2.5008 g). The diene interacted with 1.5576 g of maleic anhydride, a dienophile, to yield
1.6475 g of cyclic alkene, 4-cyclohexene, and cis-1,2-dicarboxylic anhydride. The results of the
qualitative experiment conducted in the lab verify that crystals, or six-membered rings, are created via
cycloaddition, also referred to as a Diels-Alder reaction. Additionally, the average yield of the reactions—
68.12 percent—shows the reaction's success rate. The percentage yield can be influenced by many factors
such as product loss during handling or separation.
The response turned out to be successful overall.
References
Anon, 2023. The Diels-Alder Cycloaddition. https://chem.libretexts.org/@go/page/814
Diels-Alder Reactions (2022) Master Organic Chemistry. https://www.masterorganicchemistry.com/
Harwood, L.M.; Moody, C.J. "Experimental Organic Chemistry: Principles and Practice”. Blackwell
Scientific Publications: Oxford, England, 1989, pp. 627-629.
Loudon, G.M. "Organic Chemistry", 2nd ed.; Benjamin/Cummings: Menlo Park, CA, 1988, pp. 592-600.
