In the Laboratory
An Exploration of a Photochemical Pericyclic Reaction
Using NMR Data
Sara M. Hein
Department of Chemistry, Winona State University, Winona, MN 55987
In this experiment, a photochemical [2+2] cycloaddition
reaction is investigated. Such reactions often are given as ex-
amples on paper, but are rarely investigated by students in
the laboratory (1, 2), and very few experiments involving peri-
cyclic reactions have appeared in this Journal (3–10). The
photoisomerization of cinnamic acid derivatives has been
published as an investigative experiment for a sophomore-
level organic synthesis laboratory (11, 12). Melting points
were used to identify the cinnamic acid dimer. This method
was preferred because it allowed quick identification of the
product with minimal subsequent experimentation. Because
sensitive NMR instruments and molecular modeling pro-
grams are now available, we have used these valuable tools to
characterize synthetic products, including photochemically
derived products.
Students carry out the photodimerization of trans-cin-
namic acid and derivatization of the product. Analysis of the
derivatized products and NMR spectroscopy allows students
to identify the product of the synthesis. The NMR analysis
involves molecular models and the application of coupling
constants to determine the product. Once the correct prod-
uct has been correctly identified, a mechanism can be pro-
posed. This article outlines the significance of both the
photochemical and spectroscopic aspects of the photoisomer-
ization of trans-cinnamic acid.
Experimental Overview
Trans-cinnamic acid is available from several commer-
cial sources (Aldrich Chemical Company and Acros Organ-
ics) and has been used in traditional synthetic undergraduate
organic laboratory experiments (13–15). The trans isomer is
thermodynamically stable. However, when the reagent is ex-
posed to ultraviolet light, it becomes reactive and subse-
quently dimerizes. The product is first studied by NMR
spectroscopy to propose its structure. Then its structure is
confirmed through esterification, acetylation, and computer
modeling experiments. Each step of the experiment results
in 75% yield or better.
Results and Discussion
Ring formation via dimerization of alkenes utilizing [2+2]
cycloaddition conditions is well documented (16). These re-
actions, forbidden thermally because of high activation ener-
gies, can be initiated through photochemical means.
Theoretically, π orbitals representing ethylene moieties exist
as bonding orbitals in the ground state, HOMO (highest oc-
cupied molecular orbital). For cycloaddition to occur, overlap
must occur between the HOMO and an antibonding orbital,
LUMO (lowest unoccupied molecular orbital). This is not pos-
sible under ground-state conditions (Figure 1). However, un-
der UV light, trans-cinnamic acid is able to absorb energy that
940 Journal of Chemical Education • Vol. 83 No. 6 June 2006
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promotes one molecule from its ground-state HOMO to its
excited-state HOMO, enabling overlap to occur.
The objective of this investigation is to determine which
one of eleven possible products, including stereoisomers, is
formed when trans-cinnamic acid is dimerized. Initial analy-
sis by 1H NMR spectroscopy indicates the product is sym-
metrical because of the presence of only two resonances
representing two different sets of magnetically equivalent
nuclei, corresponding to the original alkenyl protons. How-
ever, these data also support several possible head-to-tail or
head-to-head candidates. Therefore, some previous knowl-
edge about [2+2] cycloaddition reactions and radical stabil-
ity is required.
Suprafacial–suprafacial (same algebraic sign at both ends)
and antarafacial–antarafacial (opposite algebraic sign at both
ends) orbital symmetries are plausible orientations for cy-
cloaddition. In this experiment, only the head-to-tail,
suprafacial–suprafacial product is formed because the
antarafacial–antarafacial product is geometrically impossible.
Further, dimerization of alkenes can be shown to involve bi-
radical intermediates (17, 18). A biradical intermediate sug-
gests stability is the driving force behind the orientation of the
monomers, supporting the head-to-tail configuration. There are
only five possible head-to-tail cycloaddition products.
Two possible radical intermediates need to be consid-
ered: (i) a benzylic radical and (ii) a secondary radical next
to the carboxylic acid (Figure 2). The benzylic radical is sig-
nificantly more stable than the secondary radical, as observed
through energy calculations. The biradical transition state has
a reasonably long lifetime and the monomers will assume a
conformation with the least steric hindrance. In addition,
A B
LUMO LUMO
no overlap bonding overlap
HOMO of HOMO of
ground state excited state
Figure 1. HOMO and LUMO: (A) before UV irradiation and (B)
after irradiation
COOH COOH
i ii
Figure 2. Two possible radical intermediates of trans-cinnamic acid.
• www.JCE.DivCHED.org

overlap of the p orbitals stabilizes the radicals, which pre-
vents rotation of the carbon–carbon single bond, thereby re-
taining a geometrical (trans) configuration.
The trans configuration of the monomers is confirmed
by studying NMR spectra. Two doublet of doublets reso-
nances in the 1H NMR spectrum at 3.78 and 4.25 ppm rep-
resent protons on opposite faces of the cyclic portion of the
dimer. These are the only two proton resonances that are
present aside from those representing the acid and aromatic
protons. Further computational analysis supports the trans
orientation of the phenyl and acid moieties, narrowing the
number of possible dimers to two, as shown in Figure 3.
Simple esterification of the two carboxylic acid moieties
can be carried out to help students verify the presence of two
chemically equivalent groups of cyclobutyl protons. 1H NMR
analysis of the esterified dimer reveals a singlet, representing
two overlapping methyl groups. This resonance confirms that
protons H1 and H1´ and protons H2 and H2´ are magneti-
cally equivalent and not accidentally isochronous.
Truxillic acid A and B can then be differentiated. At first
glance, truxillic acid A seems more stable and may be pre-
sumed to be the correct product of the reaction because of
the greater distance between the phenyl and carboxylic acid
groups. However, the difference in energy between A and B
(4 kcal兾mol) suggests the formation of B, as determined
through molecular modeling experiments. Therefore, further
analysis is required. Elucidation of the product as truxillic
acid A is determined by 1H NMR analysis of the cyclobutyl
signals. They exist as doublets of doublets at higher fields (≥
200 MHz). Splitting patterns at low-field 1H NMR (60–100
MHz), cannot be determined but the product is possible to
determine with additional derivatization.
Formation of an anhydride and 1H NMR analysis are
used to verify the structure. By looking at the two possible
truxillic acid structures, it may be presumed that the only pos-
sible anhydride can be formed from truxillic acid B because
of the proximity of the carboxylic acid groups (Figure 4).
However, epimerization of H1 or H1´ in truxillic acid A is
possible, which also leads to formation of an anhydride. 1H
CO2H Ph CO2H H
H2′
H1 H CO2H laboratory coat are recommended. [Editor’s Note: CLIPs are
H1′
H2 H Ph available in J. Chem. Educ. for MgSO4 (2005, 82, 678) and
Ph CO2H Ph H
A B
Figure 3. Truxillic acids, two possible dimers from cinnamic acid.
Ph
Ph
O O
O Ph O Ph
O O
A B
Figure 4. The two possible anhydrides from the truxillic acid struc-
tures in Figure 3.
www.JCE.DivCHED.org • Vol. 83 No. 6 June 2006
In the Laboratory
NMR data from the anhydride derivative are used to differ-
entiate between the two possible structures. The 1H NMR
spectrum of anhydride A should reveal three different
cyclobutyl resonances with an integration of 1:2:1. The 1H
NMR spectrum of the anhydride B would reveal only two
separate resonances with a 1:1 ratio. The number of reso-
nances (three) is clear at both high-field and low-field NMR.
This supports the original assumption that A is the correct
product.
Homonuclear decoupling experiments can be carried out
to identify the cyclobutyl proton resonances, if desired. The
unusual coupling constants observed require homonuclear
decoupling experiments to determine the identity of each
proton. These coupling constants can be confirmed by sev-
eral published tables (19).
Experimental Procedure
It is recommended that this experiment (20) be carried
out in conjunction with other laboratory experiments. The
first laboratory period involves the preparation of the reaction
flask for photodimerization. This requires only 30 minutes,
with an additional hour for evaporation. The photo-
dimerization is allowed to proceed for at least two weeks. The
dimer is then derivatized by two methods, esterification and
acetylation. Esterification requires 1.5–2 hours. Acetylation
requires 2–2.5 hours. Subsequent spectroscopic analyses could
be carried out concurrently with other procedures to allow
each student some instrument time. Each step results in
≈ 75% yield. A high-field NMR spectrometer at 200 MHz
or greater is most useful. However, elucidation is also possible
with a lower-field instrument. Mechanistic studies could be
integrated into a laboratory investigation without a
spectrometer if the NMR data are provided to the students.
Sun lamps capable of emitting a wavelength of 273 nm are
required.
Hazards
Trans-cinnamic acid and magnesium sulfate are mild ir-
ritants. Tetrahydrofuran, hexanes, and toluene are flammable
and can be inhalation hazards. These solvents should be used
in the hood. DMSO-d6 and CDCl3 are carcinogens and can
be readily absorbed through the skin. Gloves, goggles, and a
hexane (2001, 78, 587, 1021, 1593).]
Experimental
Cinnamic Acid Dimer
Trans-cinnamic acid (1.5 g) is added to a 125-mL Er-
lenmeyer flask with 2–3 mL of tetrahydrofuran (THF). The
acid is dissolved by heating the flask over a steam bath. Once
the solution is hot, the flask is rotated to allow the solution
to coat the sides and bottom evenly. Excess THF is drained
by inverting the flask in a hood for an hour and a cork is
added. The inverted flask is then placed in front of a halo-
gen sun lamp (λmax = 273) for 15 days and rotated every 2–
3 days. The white solid is recrystallized in toluene (2.5 g,
85.0%). 1H NMR data are acquired in DMSO-d6.
• Journal of Chemical Education 941
 In the Laboratory
Ester Derivative
One gram of the isolated dimer, 5 mL of methanol, and
3 drops of sulfuric acid are added to a 25-mL round-bottom
flask. The mixture is allowed to reflux for 1.25 hour, cooled,
and then 13 mL of water and 13 mL of diethyl ether are
added. The aqueous layer is removed and the ether layer
washed with saturated NaHCO3 solution. The ether layer is
dried over MgSO4, filtered, and evaporated. The solid is re-
crystallized using hexane (1.05 g, 94.7%). 1H NMR data are
acquired in CDCl3.
Anhydride Derivative
One gram of the isolated dimer, 150 mg of sodium ac-
etate, and 1 mL of acetic anhydride are added to a 10-mL
round-bottom flask. The mixture is allowed to reflux for 1.5
hours, cooled, and H2O is added dropwise until the remain-
ing acetic anhydride has been hydrolyzed. Additional H2O
is added. The reaction mixture is transferred to a separatory
funnel using an additional 10 mL of H2O. The entire reac-
tion mixture is partitioned between water and methylene
chloride (5 mL). The organic layer is washed with saturated
NaHCO3 solution, dried over MgSO4, filtered, and concen-
trated to approximately 1 mL. Ice-cold ethanol (2 mL) is
added to the mixture to induce crystallization. The solid is
recrystallized using hexane (0.86 g, 66.6%). 1H NMR data
were acquired in CDCl3.
Molecular Modeling Data
Molecular modeling calculations were performed using
Hyperchem 7. The two structures were studied for geometry
optimization. The resulting energies of the truxillic acids were
A = ᎑4265 kcal兾mol and B = ᎑4269 kcal兾mol. Radical ener-
gies were ᎑2152 kcal兾mol and ᎑2175 kcal兾mol for the car-
bonyl (ii) and benzylic (i) radicals, respectively.
Conclusion
This experiment encourages students to determine the
product of a cycloaddition reaction based on mechanistic ra-
tionale and NMR data. Molecular modeling will support the
elucidation process. Although the energy difference in the two
possible truxillic acids is minimal (4 kcal兾mol), it can be ex-
plained that truxillic acid A is formed because the activation
barrier of the HOMO energy transition is less than B.
W
Supplemental Material
Instructions for the students and notes for the instruc-
tor are available in this issue of JCE Online.
942 Journal of Chemical Education • Vol. 83 No. 6 June 2006
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• www.JCE.DivCHED.org