Frances Wong, Section 24, TA: Gracia

CHEM 118-03 Thermodynamic and Kinetic Control Georgetown University

Introduction
Reactions are easily influenced by many factors, whether it is the varying properties of
the reactants, or surrounding environment. In a Diels Alder reaction (pericyclic [4+2]
cycloadditions), where a conjugated diene and a substituted alkene, or a dienophile, react to form
a substituted cyclohexene, there can be two very different products dependent on the reaction
pathway taken, specifically either kinetic, or thermodynamic. A cyclic diene forms tow
geometric isomers, named endo and exo, as shown in Figure 1. Kinetic control of the reaction

Figure 1: Mechanism of Diels Adler Reaction between cyclopentadiene and maleic anhydride

favors the endo, as the major product, while the thermodynamic control of the reaction favors the
exo, as the major product.1 In the former, it is because the most favorable position, where the p
orbitals of the substituent on the dienophile overlap with that of the diene is assumed. In the
latter, it is because added energy due to heat allows the transition state to stabilize. This
experiment is designed to observe the effects of temperature on the type of product that would be
produced from the reaction. With cylcopentaidene and maleic anhydride, the reaction that
proceeds at room temperature should proceed rapidly, due to the kinetic control, and form the
endo product. Elevated temperatures should therefore proceed rapidly, due to the thermodynamic
control, stabilizing the transition state of the product, forming the exo product. The goal of the

Frances Wong, Section 24, TA: Gracia

CHEM 118-03 Thermodynamic and Kinetic Control Georgetown University
experiment is to synthesize a fused, bicyclic compound by a [4+2] pericyclic addition reaction,
and then to confirm success with GCMS and melting point analysis.
Procedure
Cyclopentadiene (5.0 mL, 0.0595mol) in a three necked round bottom flask, with a spin
bar, was cooled in an ice bath. Maleic Anhydride in 1,2 dichloroethane (14.8mL, 0.0595mol)
was slowly added to the solution while stirring. The mixture continued to stir in the ice bath for
another five minutes. After which, a drop of the product of this reaction was used to run a CIGCMS, by diluting the solution in dichloromethane (~1.5mL). The thermowell then replaced the
ice bath and the mixture was refluxed with stirring for one hour. A drop of this product from this
rection was used to run a CI-GCMS, by also diluting the solution in dichloromethane (~1.5mL).
Excess solution was dried using a stream of nitrogen gas. The resulting crystallized product was
then dissolved in a 1:1 mixture of hexanes:ethyl acetate (~4-5mL) in a hot water bath. Once
dissolved, remove from the hot water bath, and let it re-cool to room temperature to recrystallize.
To optimize yield, place the product in an ice bath. Then, the product was vacuum filtered to dry
the crystals. A sample of it was used to determine melting point using Mel-Temp.
Given a 4M maleic anhydride in 1,2-dichloroethane, the volume of the solvent used was
calculated by the following to result in a 1:1 reaction with 5mL of cyclopentadiene:
Table 1: Molar Mass and Density Values
Solvent
Molar Mass (g/mol)
Cyclopentadiene
66.01
Maleic Anhydride
98.06
Endo Product
164.0

Density (g/mL)
0.786
1.480

Frances Wong, Section 24, TA: Gracia

CHEM 118-03 Thermodynamic and Kinetic Control Georgetown University

where V stands for volume, stands for density, m stands for mass, and Mm stands for molar
mass. To calculate the theoretical yield, the following calculations are done, using the values
calculated from above and from values listed in Table 1.

To calculate, the percentage yield equation 1 can be used:

(1)
To calculate the ratio of kinetic product and thermodynamic product, equation 2 can be used:

ratio =

A
A

kinetic

(2)

therm

where

A is the integrated area under the peaks of both kinetic and thermodynamic products.

Results

The mass of the product was 4.24g. Therefore, using equation 1, the percentage yield of
the product is 43.4%, as shown in the sample calculation below.
Sample Calculation:

Frances Wong, Section 24, TA: Gracia

CHEM 118-03 Thermodynamic and Kinetic Control Georgetown University
The melting point analysis showed that the melting range is 132C - 142C after a
thermometer calibration of 1C was subtracted. This correction factor was determined using the
following equations:

Correction = Tact Tmeasured

Correction = 100 C 101 C = 1 C
where Tact is the boiling point of water after pressure correction and Pmeasured is the measured
atmospheric pressure, and Tmeasured is the measured
temperature of boiling water using the
thermometer.
The gas chromatography-mass spectra (GCMS) are shown in Appendix A and Appendix
B of the thermodynamically controlled and kinetically controlled reactions respectively. On both
mass spectra, there were two significant ion peaks at 164.7 m/z corresponds to that of the
molecular ion of the exo- and endo-product, and another at 65.9 m/z corresponds to the
cyclopentadiene. The GCMS collected from the kinetically controlled reaction showed a ratio of
1.85:1 of kinetic:thermodynamic product, while the thermodynamically controlled reaction
revealed a ratio of 1.74:1. These ratios were calculated by the use of equation 2, as in the
following sample calculation:
Sample Calculation:

ratio =

A
A

kinetic
therm

ratio =

205854
= 1.85
111536

Discussion

The experiment
resulted in a percentage yield of 43.3% after refluxing the mixture for an
hour. Under these conditions, the product yielded should be the exo-product, as the added energy
from heating the solution should have caused the transition state to stabilize. Since endo- and
exo- products are a pair of diastereomers, they have different physical properties that can

Frances Wong, Section 24, TA: Gracia

CHEM 118-03 Thermodynamic and Kinetic Control Georgetown University
distinguish between the two, like melting point. The melting point analysis showed a melting
range of 132C - 142C. This range is below the literature melting point values of both the endoproduct (145C) and the exo-product (165C), and is closer to that of the endo-product.1 Given
the broad range in melting point, it is unlikely that the product from the thermodynamically
controlled reaction was mostly endo-product. In fact, the broad range suggests that there were a
lot of impurities. This could be due to contamination from glassware, and not recrystallizing
slowly enough to allow all the impurities to escape.
As shown and annotated in Appendix A and B, there are two peaks labeled the kinetic
product and the thermodynamic product. The peak on the left is the thermodynamic product,
because it became more stable with time and temperature. On the spectrum, there are two
significant peaks that have corresponding molecular ion peaks at 164.7 m/z. The peak from the
thermodynamically controlled reaction had an integrated area of 85832 that corresponds to the
thermodynamic product and an integrated area of 150058 that corresponds to the kinetic product.
Similarly for the kinetically controlled reaction, the peak had an integrated area of 111536 and
205854 that corresponds respectively to the thermodynamic and the kinetic product. The other
peaks shown are most likely due to leftover solvents and starting materials. The ratios of kinetic
product and thermodynamic product in the thermodynamically and kinetically controlled
reaction are 1.74 and 1.85 respectively. This supports the fact that heat favors the
thermodynamic product to be the formed, as the cold reaction increased the ratio, which means a
lessened yield of the thermodynamic product was formed before reflux. Although the ratio
supports that, the ratios are rather similar, ad in both reactions, the more abundant product was
the kinetic product. The similarity of the ratios is probably due to sources of error, such as not
sealing the round bottom flask, while refluxing, which may have boiled the solvent away and

Frances Wong, Section 24, TA: Gracia

CHEM 118-03 Thermodynamic and Kinetic Control Georgetown University
dried it out, affecting the results of the experiment. However, the abundance of the kinetic
product is most likely because less energy is required for the formation. The spectrum also
showed another significant peak at 65.9 m/z, along with that on 164.7 m/z. The latter one
corresponds to the molecular ion peak with added hydrogen, which is due to the chemical
ionization utilized, that is gentler than that of the electron impact. The former one at 65.9 m/z
corresponds to the cyclopentadiene cation, which is left over as a starting material, or is a
fragment from the experiment.
Conclusion
Based on the observations and data, it does not fully support that the system was under
thermodynamic control, or the kinetic control under the conditions studied. It supported the cold
reaction was under kinetic control, as the GCMS revealed there were more of the endo-product.
However, the same was revealed in the GCMS of the thermodynamically controlled reaction, as
the majority was also the endo-product, although there indicated to be of the exo-product formed.
The melting point range also supports this, as it was close to the melting poing of the endoproduct, but the analysis does not yield a convincing argument due to the broad range. In the
future, the experiment could be further improved by allowing the thermodynamically controlled
reaction to go to completion, by refluxing the mixture for a longer time period.
References
1. Schamrt, I.M.; Knot-Tso, M.E. J. Chem. Ed. 2004, 81, 1633-36