Introduction
The Diels-Alder reaction is one of the most synthetic reactions in organic chemistry. In this experiment, a
reaction between anthracene and maleic anhydride is performed via a Diels Alder reaction to yield 9, 10-
dihydroanthracene-9, 10-α, β-succinic anhydride. A Diel’s-Alder reaction is defined by the addition of 4Π
+ 2 Π electrons to form a six membered ring. A diene has 4 Π electron components. A diene is electron
rich and acts as the nucleophile. The dienophile has 2 Π electrons and functions as and electrophile.
Dienophiles have electron withdrawling groups attached to them. In this experiment Anthracene is used
as the diene and Maleic Anhydride is used as the dienophile. Maleic Anhydride is an excellent dienophile
because two strongly electron-withdrawing groups are attached to the double bond. And the Fig.1 shows
the Diels- Alder reaction between anthracene and maleic anhydride.
O
O H
8 9 1 O
2 H
7 O
+ O
6 3
5 10 4
O
anthracene maleic
annhydride
Figure1: Alder reaction between anthracene and maleic anhydride.
Interaction of diene LUMO and HOMO in a suprafacial [4+2] cycloaddition reaction.
The Diels-Alder reaction is a concerted (one step) reaction between a diene and a dienophile
to form a cyclohexene ring. In this Diels-Alder reaction, a double bond (dienophile) adds to a conjugated
diene to form an unsaturated six-membered ring (a cyclic shift of electrom in diene). One new pi bond
and two new sigma bonds are formed when the dienophile attacks the diene.
The diene need to be in the s-cis conformation to yield the cyclic product because if the diene is
on the s-trans conformation, number 1 and 4 carbon will be too far away from each other to react with
the dienophile. So, if a conjugated is locked in a s-trans conformation, it cannot undergo a Diels- Alder
reaction. The product that will be produced with anthracene and maleic anhydride may have two
possible products of exo adduct and endo addcut. The product 9, 10-dihydroanthracene-9-10-α, β-
succinic acid anhydride is an endo product. If 1, 4-adduct of maleic acid and anhydride forms it will be
the endo adduct form of the product will be in much greater abundance than the exo adduct form.
Procedure:
“The procedure given in the UOIT CHEM 2120 (15 th March, 2013) laboratory manual
(Experiment # 7: Diels-Alder Reaction with Anthracene) was followed without any significant
changes”.
Data and Result
Compound Amount (g) MW(g/mol) Moles Stoichiometry
Anthracene 0.40 178.23 2.24 x 10-3 Diene
Maleic anhydride 0.20 98.06 2.03x 10-3 Limiting reagent
(nucleophile)
Xylene 5 ml ( 4.34 g) 106.07 4.09x10-2 Solvent ( excess)
Crystallized product:
9,10- 0.3991 276.29 1.44x10-3 Yield =
dihydroanthracene
-9-10-α,β-succinic
acid anhydride
(Note: yield = {mol product / (mol limiting reagent x 1 mol product / 1 mol reactant)} x 100%)
Example Yield Calculation:
Yield = {1.44 x 10-3moles / (2.03 x 10-3moles x 1 mol product / 1 mol reactant)} x 100%) =
70.9% ~ 71%.
Melting point analysis result:
1. Crystallized Product(9, 10-dihydroanthracene-9,10-α, β-succinic anhydride) Melting point
range : 257-259⁰C
2. Standard Product(9, 10-dihydroanthracene-9,10-α, β-succinic anhydride) Melting point
range : 261⁰C
Figure 3 – 1H NMR Spectra of 9, 10-dihydroanthracene-9,10-α, β-succinic anhydride.
7.21
1 H N M R s tu d e n t p r o d t W 1 3
3.52
1.0
7.22
4.83
3.51
0.9
7.20
7.19
0.8
7.33
0.7
7.38
7.48
Normalized Intensity
4.83
8.44
0.6
0.5
8.00
8.03
0.4
0.3
0.2
0.1
0
0.74 1.50 1.492.18 2.07 4.23 2.05 2.00
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
7.21
1 H N M R s tu d e n t p r o d t W 1 3
1.0
7.22
0.9
7.20
7.20
7.19
0.8
7.33
0.7
7.38
7.48
7.46
Normalized Intensity
7.39
7.34
0.6
7.35
7.40
7.26
0.5
7.47
0.4
0.3
0.2
0.1
0
1.49 2.18 2.07 4.23 0.03
7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00
Chemical Shift (ppm)
Figure 4 – 13C NMR of 9,10-dihydroanthracene-9,10-α, β-succinic anhydride
124.63
1 3 C N M R s tu d e n t p r o d t W 1 3
48.22
127.98
1.0
0.9
0.8
128.39
0.7
76.94
Normalized Intensity
77.25
77.58
0.6
170.67
138.31
45.65
140.85
0.5
0.4
131.91
0.3
0.2
0.1
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
124.63
1 3 C N M R s tu d e n t p r o d t W 1 3
127.98
1.0
125.43
0.9
0.8
128.39
127.38
0.7
125.57
Normalized Intensity
0.6
138.31
140.85
0.5
0.4
126.44
131.91
0.3
0.2
0.1
142 140 138 136 134 132 130 128 126 124 122
Chemical Shift (ppm)
Figure 4: IR of pure Maleic anhydride
Figure 5: IR of Anthracene
Figure 6: NMR of Pure Anthracene
Figure 7: NMR of pure maleic anhydride
Discussion:
The synthesis of 9,10-dihydroanthracene-9-10-α,β-succinic acid anhydride using Diels-
Alder reaction did produced product which is which is proven by Melting point analysis and
NMR analysis. This experiment had a successful turnout. The observed melting point of the
product was 257 – 259°C. This was relatively close to the literature melting point value of
261°C. The observed melting point may have been lower because the product may still have
been wet or there may have been impurities in the product. The melting point of the compound
had a broader range of 4°C and was a little bit lower due to impurities in the product. Upon
crystallization of the product, the melting point range narrowed and was higher. Therefore,
crystallization was successful in purifying the product. However, the melting point was close to
the literature value, thus indicating that the obtained product was 9,10-dihydroanthracene-9-10-
α,β-succinic acid anhydride and the reaction was successful. As well as, if infrared spectrum of
the product is examined .They were then compared with the infrared spectrum of the product
obtained in the experiment. Upon comparison, it was found that the spectrum of the product had
similarities with both the spectrum of anthracene and maleic anhydride, as should be expected
since the Diels Alder product is a combination of both anthracene and maleic anhydride.
The reaction synthesized 9,10-dihydroanthracene-9,10- α,β-succinic anhydride with a
71% yield. The yield was lowered because not all of the reactants reacted with each other. The
reaction was limited to the amount of maleic anhydride used. A small amount of product was
lost in the crystallization.Product may be lost during taking out the whole product from Hirsch
funnel leaving some amount of product in it, reducing the yield, leaving some product residues in
the flask and negligiency such as spilling the product while weighing it.
In this experiment, IR not a good method for distinguishing product (1) which is 9,10-
dihydroanthracene-9-10-α,β-succinic acid anhydride from the reactant maleic anhydride because
the product(1) and the reactant used (maleic anhydride) are structurally too similar( have same
functional groups) except benzene functional group which is only present in product (1) not in
maleic anhydride. As well as, the product IR spectra would be difficult to distinguish from the
starting materials because the only different functional group that is generated by the Diels alder
reaction is a sp3 methyne (tertiary) carbon'.
The 1H-NMR of product (1) shows four aromatic multiplet signals (two multiplets are
overlapped at 7.2 ppm) and two non-aromatic peaks. This spectrum is consistent with the
product (1) molecule and not with either of the reactants because as compared to our product we
should get 2 signal for the benzene ring protons in Fig and we got four signals in range of 6 to
8.5 ppm region.Two signals represent to the two benzene ring in product and other two signal
represent the chemical shift of protons (H’s) bonded to two aromatic rings (in general the
chemical shift for H-Ar is in between 6-8.5). Other kind of protons do not resonate in this
region,so signals in this region of an H NMR spectrum indicate that the compound probably
contains an aromatic ring.The other two non-aromatic peaks in product (1) just represent
Hydrogens that are bonded to an ester (H-C-OC=O). There is one peak at 4.83 and one at 3.52,
even though there H’s should be coupled. This violates the n+1 rule.It is not consistent with the
any of the reactant because in anthracene we have H-Ar signal in range of 6-8.5 but we don’t
have signal of ketone around 4.85 and same with maleic anhydride.So, we can say that the given
spectrum is consistent with the product(1) but not any of the reactant.Yes, there might be side
product or impurities present in the student sample, which could show presence of maleic
anhydride. Other products which could be present are anthracene, xylene, etc.
