Experiment 2 POST-LAB REPORT 1

Experiment 2: Diels-Alder Synthesis of9,10−dihydroanthraceno−9,10−endo− α, β−succinic

anhydride

Claudia Zamora Cisnero

T.A Ning Shen

University of South Florida: CHM2211L.903

January 16, 2021

POST-LAB REPORT 2

Introduction

In this experiment, a Diels-Alder reaction was performed to synthesize the compound

9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride. Diels-Alder reactions were

first explored by the German chemists Hurt Alder and Otto Diels. Their work was significant

because they researched many different types of dienes that would form specific cyclic

compounds when reacted with olefins. As such, the Diels-Alder reaction is one of the most

important reactions in the field of organic chemistry. The Diels-Alder reactions are considered

one step (concerted) reactions because they involve the cyclic rearrangement of electrons,

resulting in bonds breaking and forming simultaneously. Due to this, Diels-Alder reactions are

also categorized as pericyclic reactions that are stereospecific1.

The important reaction requires a dienophile containing electron-withdrawing groups and

a diene containing electron-donating groups. Since Diels-Alder reactions are stereospecific, the

predominating isomer is the one including the more overlap of π electrons in the transition state.

The endothermic stereochemistry is favored over the exothermic stereochemistry in the product,

as the endo isomer contains the greatest overlap of π electrons as compared to the exo isomer. As

a result, the endothermic isomer is the major product of this reaction. Applying this theory, this

experiment attempted to synthesize 9,10−dihydroanthraceno−9,10−endo− α, β−succinic

anhydride, using anthracene as the diene and maleic anhydride as the dienophile. In order for

this reaction to be successful, optimal thermal conditions are required. A source of heat must be

utilized for this reaction to proceed and yield the desired product1. Another simple example of a

Diels-Alder reaction is the synthesis of cyclohexane from the reaction between 1,3-butadiene and

ethene2.
POST-LAB REPORT 3

Mechanism

Figure 1: Synthesis of
9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride

Side Reactions

I.

II.

Figure 2: Side reactions during synthesis of 9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride

Experiment Procedure

Figure 3: Procedure for the synthesis of 9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride

POST-LAB REPORT 4

1) Round Bottom Vial 2) Reaction Mixture in 3) Product

Vial

+ magnetic stir bar

+ remove vial + obtain mass

+ 0.6 g anthracene
+ cool to room
temperature + calculate percent yield
+ 0.3 g maleic anhydride
+ observe
crystallization + determine melting
+ 0.6 ml xylenes point

+ collect crystals with

vacuum filtration
+ obtain 1HNMR
+ connect vial to a water
cooled connector with
CaCl2
+ wash crystals with
cold xylene

+ reflux and stir for 30

minutes
+ allow vacuum to pull air
through filter

+ dry

Chemicals Used

Table 1: Chemicals used in the synthesis of 9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride

ANTHRACENE
Physical and Chemical Properties
Structure formula molar mass boiling point
C 14 H 10 178.2 g/mol 339.9 °C

melting point density Hazards

POST-LAB REPORT 5

 hazardous if inhaled
 toxic if ingested
215.8 °C 1.25 g/mL  skin and eye irritant

MALEIC ANHYDRIDE
Physical and Chemical Properties
Structure formula molar mass boiling point
C 4 H 2 O3 98.06 g/mol 202 °C

melting point density Hazards

 toxic if inhaled
52.6 °C 1.48 g/mL  toxic if ingested
 skin and eye irritant
 corrosive
 combustible

9,10-DIHYDROANTHRACENO-9,10-ENDO-α , β-SUCCINIC ANHYDRIDE

Physical and Chemical Properties
Structure formula molar mass boiling point
C 18 H 12 O 3 276.3 g/mol 484 °C

melting point density Hazards

 skin and eye irritant

 toxic if inhaled
260 °C 1.3 g/mL  toxic if ingested

Experiment Results

Table 1: Results of the synthesis of 9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride

Mass of the desired product 0.778 g
Melting point of the desired product 260 °C
Percent Yield 91.2%
Percent Yield Calculations:

1 mol C 14 H 10 1 mol C18 H 12 O3

0.6 g C14 H 10 × × =0.000337 mol C18 H 12 O3
178.2 g/mol 1 mol C14 H 10
POST-LAB REPORT 6

1 mol C 4 H 2 O 3 1 mol C18 H 12 O 3

0.3 g C 4 H 2 O 3 × × =0.000306 mol C18 H 12 O 3
98.06 g/mol 1 mol C 4 H 2 O3

 Limiting reagent is C 4 H 2 O3 (maleic anhydride)

1 mol C 4 H 2 O 3 1 mol C18 H 12 O 3 276.3 g/mol

0.3 g C 4 H 2 O 3 × × × =0.85 g C 18 H 12 O 3
98.06 g/mol 1 mol C 4 H 2 O 3 1 mol C18 H 12 O 3

 Theoretical Yield for the product is 0.85 g

Actual Yield 0.778 g C18 H 12 O3

× 100 %= ×100 %=91. 2 %
Theoretical Yield 0.85 g C18 H 12 O3

1
H-NMR Spectrums for Diels-Alder Product

Figure 4. 1H-NMR (chloroform as solvent) of the final desired product

POST-LAB REPORT 7

O
O
O

8 7 6 5 4 3 2 1 0
PPM
Figure 5. The theoretical 1H NMR spectrum of the desired product.

Discussion

During this experiment, 0.778g of 9,10−dihydroanthraceno−9,10−endo− α,

β−succinic anhydride were collected. After careful calculations, the percent yield was

determined to be 91.2%. Such a high percent yield confirms that the overall reaction was

efficient and that the final product was pure. A percent yield over 50% is always a positive sign

that indicates relative success. Melting point values serve as a method of identification for

experimental compounds. As such, an accurate melting point can identify the obtained

compound and also indicate an efficient synthesis. In this case, the resulting crystals presented a

melting point that was identical to the literature value, identifying the compound as 9,10−

dihydroanthraceno−9,10−endo− α, β−succinic anhydride. Moreover, the sample displayed

a melting point of 260 °C, which is the same as the literature value. The accurate melting point

and elevated percent yield also suggest that the side reactions that could have interfered with the

formation of the desired product were kept under control. Thus, in quantitative terms, this

reaction was proficient and successful.

POST-LAB REPORT 8

Additionally, the 1HNMR spectrum of the final product was obtained for analysis and

comparison (Figure 4). The theoretical 1HNMR spectrum of the desired product was also

included for reference (Figure 5). After examining both spectrums carefully, some similarities

can be noted. For example, the obtained 1HNMR spectrum displays major peaks at 8.01, 2.00,

and 1.98 ppm respectively, while the theoretical spectrum displays four major peaks around 7.3,

7.2, 4.4, and 3.4 ppm. However, there are some discrepancies between the theoretical and

experimental values which could have been caused by diverse reasons. For example, impurities

in xylene and/or the diene or dienophile could have affected the environment of protons in the

resulting molecule and therefore the peaks in the spectrum. Furthermore, the accidental addition

of water or any other substance containing hydrogen could have interfered with the 1HNMR

spectrum and produced stronger peaks. Nonetheless, the high percent yield and accurate melting

point suggest that any impurity was kept minimal and that the resulting compound is precisely

9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride.

Conclusion

In conclusion, the Diels-Alder reaction performed in this lab employed anthracene and

maleic anhydride to synthesize 9,10−dihydroanthraceno−9,10−endo− α, β−succinic

anhydride. This process included the vacuum filtration and crystallization (with xylene) of

the final product, which was then analyzed for melting point and NMR spectrum. As

previously discussed, the melting point of the compound was determined to be 260°C,

which is the same melting point value found in the literature. This demonstrates that the yielded

product was indeed 9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride; and

that the experiment was exposed to none or minimal systematic/random error. Moreover, the
POST-LAB REPORT 9

percent yield of the reaction was calculated to be 91.2%, which also appoints to efficiency

and minimal systematic/random error. Lastly, the 1HNMR spectrum of the resulting

substance helped characterize the compound’s structure and consider impurities that could have

affected the compound’s proton arrangement.

Diels-Alder reactions are used in many important areas, especially in the field of

biochemistry and drug production. For example, Diels-Alder reactions are utilized in the

manufacture of cyclopentadiene, a compound that is used to facilitates the formation of

norbornenes (a type of monomer), and consequently the production of polymers. Furthermore,

Diels-Alder reactions are a significant part of the production of vitamin B6, an important

supplement that provides essential nutrients6. The purpose of this experiment was to synthesize

9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride via a Diels-Alder reaction,

after analyzing the experimental data and the theoretical framework of the experiment, it is

fair to conclude that the synthesis was carried out efficiently and that this experiment

accomplished its main objective.

POST-LAB REPORT 10

References

[1] Weldegirma, S. (2020) 9,10−dihydroanthraceno−9,10−endo− α, β−succinic anhydride.

Experimental Organic Chemistry. pg. 83-86.

[2] Hunt, D. (n.d.). Chapter 10: conjugation in Alkadienes and Allylic Systems. Retrieved

January 17, 2021, from http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch10/ch10-

5.html

[3] Anthracene. National Center for Biotechnology Information. PubChem Compound Database.

U.S. National Library of Medicine.

[4] Maleic Anhydride. National Center for Biotechnology Information. PubChem Compound

Database. U.S. National Library of Medicine.

[5] Anthracene. National Center for Biotechnology Information. PubChem Compound Database.

U.S. National Library of Medicine.

[6] Diels–Alder reaction. (2021, January 03). Retrieved January 22, 2021, from

https://en.wikipedia.org/wiki/Diels%E2%80%93Alder_reaction#Applications