C

Duke University - Organic Chemistry Laboratory

Lab

DIELS-ALDER REACTIONS1
Background
Introduction
The Diels-Alder reaction is a very synthetically useful cycloaddition that results in

Reading Assignments

high yields of cyclohexene products with high stereo- and regioselectivity. In a typi-

Techniques:

cal reaction, the substrates consist of an electron rich diene in the s-cis configuration

Filtration: Fessenden2, p. 29-32

and an alkene substituted by one or more electron withdrawing groups (the dieno-

Reflux: Fessenden, p. 154-156

phile). One example is shown below in Figure 1.

Chemistry:
Diels-Alder: Loudon3, p. 690-700
Aromaticity: Loudon, p. 721-727

H
s-trans

s-cis

DIENE

Kinetic vs. Thermodynamic control of reactions:

Loudon, Sec. 15.4C, p. 705-707

DIENOPHILE

SUBSTITUTED
CYCLOHEXENE
PRODUCT

Figure 1. An example of a Diels-Alder reaction.

In todays experiment we will perform two Diels-Alder reactions. First, you will react the diene furan 1 with the
common dienophile, maleic anhydride 2 (Fig. 2). The melting point of your product will be used to determine
whether the exo or endo stereoisomer is the major product with further characterization via IR spectroscopy.
O
O +

O
O

O
1

THF
RT

O
3a

3b

Figure 2. The formation of 7-oxobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride.

In the second part of this experiment, anthracene 4 and maleic anhydride 2 react to give Diels-Alder Adduct 5 (Fig.
3). You will use NMR as well as melting point data to characterize this second product.
O
O
+

H
H

O
2

Figure 3. The formation of dihydroanthracene succinic anhydride.

Safety Issues
Anhydrides react quickly with water to form acids, if you spill any anhydride on yourself wash it off immediately.
Standard uses of gloves, safety glasses, and pipettes are to be observed. See Lab 1 or consult your TA for details.

A m a n d a K a s p e r, P h . D . O r g a n i c L a b o r a t o r y M a n a g e r 1 2 2 5 F r e n c h F a m i l y S c i e n c e C e n t e r

Procedure
PART 1. Preparation of a 7-Oxanorbornene Derivative SHOULD HAVE BEEN COMPLETED DURING LAB 1.
Step one Synthesis of 7-oxobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride via the reaction of furan and maleic anhydride.
1.

Charge a 50 mL round bottom flask (RBF) with 5g of maleic anhydride. The maleic anhydride may have to be
ground into a powder with a mortar and pestle. If so, two groups may want to join together in grinding a larger
briquette and share the resulting ground maleic anhydride. Please be sure to clean the mortars and pestles with
acetone when you are finished.

2.

To the 50 mL RBF containing the maleic anhydride add 15 mL of tetrahydrofuran and swirl until the maleic anhydride dissolves completely.

3.

Add 3.3 mL of furan, swirl to mix thoroughly, and stopper the RBF with a rubber septum.

4.

Clearly label your flask with the following information:

5.

a.

Both lab partners names

b.

Lab section number

c.

Maleic anhydride + furan + THF

Place the RBF in a beaker in your sections box and allow the reaction mixture to stand in until the following lab
period.
Stop the rest of the procedure will be performed at the next lab meeting.

H
! int: To maximize efficiency, set up the 20 minute reflux right away then work up your product from last
week.
PART 2. Preparation of Dihydroanthracene succinic anhydride.
1.

Charge a 50 mL round bottom flask with 2g of anthracene, 1.1g of maleic anhydride, 25 mL of dry xylene, a magnetic stir bar and a few boiling stones. Fit a reflux condensor into the flask.

2.

Place the round bottom flask in the metal heating tray on a hotplate, cover the RB with aluminum foil and heat to
reflux with stirring for 20 minutes. What does reflux mean?
Now is a good time to work up the furan/maleic anhydride adduct.

3.

Allow the solution to cool completely and collect the crystalline product using vacuum filtration. Allow the vacuum to pull air through the product for 5-10 minutes to facilitate drying.

4.

Dry the product further by pressing the solid between dry filter paper.

5.

Weigh your product, calculate a percent yield, and measure the melting point range. Obtain an IR spectrum of
your product.

ONLY ONCE YOU HAVE GATHERED ALL OF THE REQUIRED DATA dispose of the product in the waste container labeled Solid Waste in the common hood.

D u k e U n i v e r s i t y!

Lab 3: Diels-Alder Reactions

PART 1. (**Continued from last week**)

Step two Isolation of 7-oxobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride.
6.

Collect the crystalline product using vacuum filtration. Wash with a small amount (<5 mL) of ice-cold THF. Allow the vacuum to pull air through the product for 5-10 minutes to facilitate drying. Dry the product further by
pressing the solid firmly between dry filter paper

7.

If you do not have crystals do not despair. Try placing the flask in an ice bath, scratching the side of the flask
firmly (but not too firmly) with the end of the glass stir rod (if this is your first scratching experience it is best to
work with your TA on this one), or seed the mixture with a few product crystals from one of your neighbors.

8.

Weigh your product, calculate a percent yield, measure the melting point range and analyze the NMR spectra
provided on Sapling. You may choose to analyze the product by IR if you wish.

9.

ONLY ONCE YOU HAVE GATHERED ALL OF THE REQUIRED DATA dispose of the product in the waste container labeled Solid Waste in the common hood.

Prelab Assignment
Objective: include a general description of the purpose of the lab. Draw out the reaction and mechanism for both
Diels Alder reactions. Important: make a prediction as to whether the endo or exo product will be favored in the
reaction of furan with maleic anhydride and briefly describe your reasoning.
Table of reagents and products: Include a table like the one shown below and include columns for the EXACT
amounts of reagents used (in grams or mL AND mols).

Separation scheme: Not required this week.

Procedure: Reference this lab handout.

D u k e U n i v e r s i t y!

Lab 3: Diels-Alder Reactions

In-Lab Notebook
Procedure and Observations record EXACT amounts of reagents used (use table similar to one shown above),
observations, and any changes you have made to the written procedure. This should be written directly in your
notebook while you are in the lab.
All information above should be written directly into your lab notebook. The duplicate pages will be turned in to
your TA at the end of the lab.
All information below will be included on the Post-Lab Report and does NOT have to be written separately in
the notebook. You may choose to work through your calculations or organize your ideas for the discussion, etc.
in the notebook, but this information is not required in the notebook.

Post-Laboratory Report
Complete the report as directed below.

References
Parts of this procedure have been adapted from: Roy, C.P., Sebahar, H.L. Organic Chemistry Laboratory Handout, Duke University, 2005, 2008; France, M., Alty, L. and Earl,
T.M., J Chem Ed., 76, 5, 1999, pg. 659; and Campbell, B., and Ali, M., Organic Chemistry Experiments, Brooks/Cole Publishing 1994.
1

Fessenden, Fessenden, Feist. Organic Laboratory Techniques, 3rd Edition. Brooks/Cole, Pacific Grove, CA, 2001.

Loudon, GM. Organic Chemistry. 5th ed. Roberts & Company Publishers; 2008

D u k e U n i v e r s i t y!

Lab 3: Diels-Alder Reactions

Chemistry 202L - Post Lab Report for Diels-Alder Reactions (Lab 3)

Name:__________________________________!

TA name/Section number:______________________________

7-oxanorbornene derivative
Balance the equation used in the reaction:

O
O +

O
O

O
THF
RT

O
O
O
3a + 3b

Calculate amount of furan (in moles) actually used (based on the amount you measured):

Calculate amount of maleic anhydride (in moles) actually used (based on the amount you measured):

The limiting reagent is: ______________________________________

Calculate theoretical yield for the 7-oxanorbornene derivative:

Calculate the percent yield for the 7-oxanorbornene derivative:

D u k e U n i v e r s i t y!

Lab 3: Diels-Alder Reactions

In the space below, draw a curved-arrow mechanism for the reaction performed in Part 1.

Appearance of isolated 7-oxanorbornene derivative:_________________________

Literature appearance:__________________________
Observed mp range:___________!

Literature mp range:___________

Show the exo-product in the space below:!

Show the endo-product in the space below:

Based on what youve learned from consulting your text or in lecture, which is the expected major product (exo/endo)?
_____________________________
Based on the analysis of your experiment, what was the major product you synthesized? (exo/endo)?
_____________________________

D u k e U n i v e r s i t y!

Lab 3: Diels-Alder Reactions

Dihydroanthracene succinic anhydride:

Balance the equation used in the reaction:
O
O
+

H
H

O
O

O
4

Calculate amount of anthracene (in moles) actually used (based on the amount you measured):

Calculate amount of maleic anhydride (in moles) actually used (based on the amount you measured):

The limiting reagent is: ______________________________________

Calculate theoretical yield for dihydroanthracene succinic anhydride:

Calculate the percent yield for dihydroanthracene succinic anhydride:

D u k e U n i v e r s i t y!

Lab 3: Diels-Alder Reactions

In the space below, draw a curved-arrow mechanism for the reaction performed in Part 2.

Observed mp range: ________________________!

Literature mp range: ________________________

Additionally:
Attach a copy of your IR spectrum for the anthracene/maleic anhydride adduct. Indicate the functional group responsible for each important peak. You may ignore the fingerprint region. Attempt to identify at least two important peaks.
Attach a copy of 1H NMR spectra of the oxanorbornene derivative. Draw the structure of the molecule directly on
the spectra and letter (Ha, Hb, Hc, etc.) the unique protons. Does the number of unique protons that you have predicted match the number from the spectra? Identify the peaks that correspond to each labeled proton.
Attach a copy of the 13C NMR spectra of the dihydroanthracene succinic anhydride. Draw the structure of the
molecule directly on the spectra and number the unique carbons. Does the number of unique carbons that you
have predicted match the number from the spectra? Identify the following four types of carbons on the drawing
and the corresponding peaks on the spectra: sp3-hybridized, quaternary aromatic carbons, non-quaternary aromatic, and carbonyl carbons.

D u k e U n i v e r s i t y!

Lab 3: Diels-Alder Reactions