Blake Andreou

CHEM 2222L
Section 15 Thursday, Bay D
February 13, 2017
Title:

Lab #2: Diels- Alder Reaction of Anthracene and Maleic Anhydride

Introduction

A Diels-Alder reaction is characterized by the formation of two carbon-carbon sigma bonds in a

single concerted step. This reaction requires two compounds: a diene and an attacking electron-
rich dienophile. This reaction is stereoselective, and its selectivity is determined by the
stereochemistry of each reactant. In the chosen reaction, anthracene was the diene and maleic
anhydride was the dienophile. These two reactants combined in the presence of xylene and heat
to form 9,10-dihydroanthracene-9,10-,-succinic anhydride. The primary product reacted with
water vapor to form an acid as time elapsed. The final product underwent IR and NMR analysis
to gauge the success of the synthesis reaction.

Procedure

This procedure was carried out as described in the CHEM 2222L Lab manual for Lab #2 with
0.503 g anthracene and 0.256 g maleic anhydride. During the cooling of the refluxed product in
the ice bath, the round bottom flask was unintentionally inverted into the ice bath. Since the
organic material is nearly immiscible with water, it was possible to retrieve the organic material
from the bath. Some error may have been made during this retrieval.

Results:

The IR spectra and HNMR analysis are attached.

Table 1: IR spectra Analysis

Wavenumber 3350 2995 1854.20 1774.22 1453.69

(cm-1)
Functional Alcohol C-H Carbonyl Carbonyl Aromatic
Group
Table 2: HNMR Analysis

Peak A B C D E F

Splitting Triplet Singlet Septet Singlet Quartet Quartet

(Doublet of (Doublet of
Doublets) Doublets)
Ppm Shift 3.45 4.85 7.23 7.27 7.35 7.40

Functional
Group Allylic Allylic Aryl Aryl Aryl Aryl

Integration 0.99 1.01 1.035 1.035 0.98 1.00

Table 3: Experimental Masses and Yields

Theoretical Yield 0.741 g

Pre-Crystallization Yield 0.110 g

Post-Crystallization Yield 0.070 g

Calculations:

% Yield = [(Actual Yield) / (Theoretical Yield)] * 100 %

Pre-Crystallization Yield = [(0.110 g) / (0.741 g)] * 100%

Pre-Crystallization Yield = 14.84%

Pre-Crystallization Yield = [(0.070 g) / (0.741 g)] * 100%

Pre-Crystallization Yield = 9.45%

Percent Recovery during Crystallization = [(0.070 g) / (0.110 g)] * 100%

Percent Recovery during Crystallization = 63.64%
Conclusion

The percent yield before the product was recrystallized was 14.84%. This suggests that either the
synthesis was not particularly successful, or that much of the organic material was lost in the ice
bath when the round bottom flash capsized. Product also could have been lost via a leak in the
condenser if it was not attached correctly. The product is soluble in xylene, and adding too much
xylene could have led to a net loss in product farther on. The recrystallization procedure was
followed more closely, and the percent of product that was retained was over sixty percent,
suggesting that the recrystallization was very successful. The analysis of the IR and NMR spectra
maintains the success of the reaction. Since Diels-Alder reactions are organic synthesis, the only
difference between the products and the reactants in these spectra are in the region where the two
products react. In IR, this would be apparent by the introduction of sp3 hybridized carbons (all
carbons in the reactants are hybridized to sp2 or sp). The introduction of the alcohol group could
hint that some of the product began to oxidize to form an acid, but considering that maleic
anhydride, a reactant, would also undergo that process in water vapor, the presence of an alcohol
is not diagnostic. In the NMR spectra, to see a difference in the products vs. the reactants, it was
necessary to look for a triplet with a shift of about 3.5. This is where the Diels-Alder reaction
actually occurred, and these hydrogens would not be triplets if the reaction did not occur. The
NMR does display a triple at 3.45, indicating a successful synthesis.

Questions:

1:

2: There was a limit of 15mL on the amount of xylene used because excess xylene would lead to
oversaturation of the product in xylene, and a net loss of product and lowering of percent yield of
the reaction.

3: The IR peak in the carbonyl region for anthracene is nonexistent. There are no oxygen
molecules. The IR peak in the carbonyl region for maleic anhydride should be a strong broad
peak, indicating the existence of the two carbonyl groups. The IR for the product should be
similar to the IR for maleic anhydride, since the two carbonyl groups remain in the product.
However, the maleic anhydride has potential for resonance which would lead to a much broader
peak. The Diels-Alder reaction removes the double bond in maleic anhydride, and therefore
stunts resonance and makes the product peak far narrower.

4: The specific peak that is not found in either of the reactants but is present in the products is a
sp3 hybridized C-H stretch. A Diels-Alder reaction functions by moving around electron density
to form two sigma bonds and break some double bonds along the way. This breaking and
remaking of bonds in this particular reaction forms sp3 hybridized carbon atoms from the new
sigma bonds, which are not present in either of the reactants.

5: Cyclopentadiene is both a dienophile and a diene, and will attack another molecule of
cyclopentadiene to form bicyclopentadiene.

6: A Diels-Alder reaction is characterized by a dienophile (maleic anhydride in this case)

attacking a cis-diene. Neither of these possible reactants are capable of making a cis-diene, due
to hybridization in the first compound and ring constraint in the second compound, making an
environment in which Diels-Alder reactions will not occur.