Discussion

In this laboratory experiment, the bromination of P-toulic acid, via the donation of
bromine from N-Bromosuccinimide, created the product of interest, 4-(Bromomethyl)
benzoic acid. To evaluate the products purity, Nuclear Magnetic Resonance (1H-NMR),
Infrared Spectroscopy (IR), percent yield and qualitative data was recorded. In the
second portion of the laboratory procedure, the rate of radical bromination of various
hydrocarbons (cyclohexane, methylcyclohexane, toluene, ethylbenzene, isopropyl
benzene and t-butylbenzene) was measured qualitatively and compared to radical
stability.
Despite some impurities shown in the 1H-NMR analysis, all signals corresponding to
protons in the product were visible on the spectrum except the one found in the O-H
acid. There were three signals in total: (, ppm) HA = 4.50 (s, 2H), HB = 7.50 (d, 2H) and
HC = 8.10 (d, 2H). HA is located one carbon away from the bromine group, deshielding
and pushing it downfield. Likewise, HB and HC are deshielded downfield, yet to a greater
extent due to their location near alkene bonds on the aromatic part of the product. H C is
the most downfield due to its proximity to the carboxylic acid. The presence of the
correct chemical signals indicates that the product was correctly synthesized via the
reaction; however, impurities cannot be ignored. P-toluic acid, the reactant, was found
at 7.87 ppm (d, 2H) and 2.38 (s, 3H). Similarly, Succinimide, an N-Bromosuccinimide
byproduct, had a signal at 2.8 ppm (s). These signals indicate that the product was not
completely isolated during vacuum filtration and may have remained crude. Since
Succinimide is water-soluble and should have dissolved when the crude product was
washed with deionized water, it may not have completely dissolved during the treatment
and remained with the pure product. Petroleum ether, which also washed the crude
solid, displayed a signal at 1.27 ppm (s). During the vacuum filtration step, the solid may
not have completely dried, thus having petroleum ether remain in the product. Two
other unidentified impurities showed signals, and they were most likely due to
contamination in the laboratory.
The IR analysis shows peaks corresponding to the bond stretches found in the product.
Six stretches, C-H (sp2, 2800-3050 cm-1), C-H (sp3, 2700-2850 cm-1), O-H (2500-2700
cm-1), C=O (1680 cm-1), C=C (1550-1610 cm-1) and C-Br (500-600 cm-1) were recorded
on the IR. Due to the presence of the C-Br stretch, bromine was found in the final
product, indicating that P-toulic acid and N-Bromosuccinimide reacted. The C-H sp2
stretch and C=C stretch were found on the IR due to the aromatic group in the product.
However, they may have also been from P-toluic if cross-comparing IR and NMR data.
The O-H and C=O stretches belong to the carboxylic acid group apart of the product. Ptoluic also has a carboxylic acid group, and due to it showing up as an impurity, it may
have contributed to these stretches. Overall, however, the stretches matched up with
those found in the final product, thus confirming it was synthesized properly, although
not entirely purely.
The percent yield for the extracted 4-(Bromomethyl) benzoic acid (0.25 g) was
calculated to be 58.1%, using p-Toluic acid as the limiting reagent. Considering that the

yield is neither too high nor too low, and that there were some impurities in the product,
the amount of impurity may not be that high. Since the product yield is at around 50%, a
majority of the product is most likely purified, with the contaminations occurring slightly
in the filtration step.
Examining the color and state changes during the heat reaction and filtration steps can
indicate the purity of the product. Initial to the experiment, P-toulic acid was a white
power, N-Bromosuccinimide was a yellow power, benzyl peroxide was a white powder,
and chlorobenzene was a colorless liquid. After mixture and during heating, the
substance was clear and had a light yellow/brown color. When the crude product
crystallized during the first filtration, it was a slightly yellow/brown solid. After washing
the crude product a second time to extract the pure product, it was then white. The
white color indicates that almost all of N-Bromosuccinimide was extracted out with the
crude product, although some the byproduct remained. P-toluic is initially a white
powder and cannot be qualitatively distinguished from the pure product. Although the
solid seemed dry, since petroleum ether (one of the washing solutions) was found
during NMR analysis, it may have still been slightly damp when analyzed.
Another issue that may have caused impurities was that the reaction occurred but did
not go to completion. Since light was used as photoredox catalysis for this reaction to
generate the bromination, if anything was obstructing the hood light, reactants may
have stayed present in the product. However, considering that the product was
identified in NMR and IR analysis, this most likely was not a major case for impurities.
When brominating various hydrocarbons in the second part of the laboratory, the trend
of most stable free radical hydrocarbons reacting quickest was tested. Tertbutylbenzene had the fastest rate of reaction (285 sec), followed by cumene (515 sec),
ethyl benzene (924 sec), toluene (1635 sec), methylcyclohexane (2543 sec), and
cyclohexane (4363 sec). This order of reaction rates was one that was predicted
because the most stable radical intermediates should want to react quicker to get to that
state.
Qualitative observation was done to correctly identify which hydrocarbon reacted the
fastest. Potassium bromide was dissolved in water, and 10 drops of HCL were added.
Bleach was then added, which turned the solution bright yellow. 2 mL of chlorobenzene
was added, and two layers of solution were formed: a yellow aqueous top layer and an
orange organic bottom layer. The bottom layer was extracted and pipetted into six test
tubes for the various hydrocarbons. Each hydrocarbon was added to its designated test
tube, and free bromine (a brown liquid) was added. When the reaction of a hydrocarbon
went to completion, it became a clear, colorless liquid, which is when data on the rate
was recorded. This color conformation indicated that the hydrocarbons were
brominated.
Similar to the first part of the experiment, the hood light was used as a catalyst for the
hydrocarbons rates of reaction. Although each hydrocarbons rate coincided with the
predicted rates, the light source may still have altered how fast or slow the rates were. If

something was obstructing the test tubes with the different hydrocarbon mixtures, then
the reaction would not go, and the rates would be incorrect.
When comparing two different hydrocarbons (tert-butylbenzene and cyclohexane), there
are a couple factors that make one a more stable radical than the other. Tert-butyl
benzene had the fastest rate of reaction due to the electron density of its methyl groups.
These groups stabilize the electron-deficient radical and in theory, the more alkyl groups
surrounding a radical, the most stable it is. This is unlike cyclohexane, which only has
hydrogen atoms surrounding ring. The hydrogen atoms cannot donate electron density
as well as tert-butyl benzene, therefore, the rate of reaction to the radical takes longer
because it is a less stable conformation. Another stabilizing factor is delocalization via
Pi bonds. Delocalization helps spread electron density throughout the molecule
(because of resonance). Cyclohexane does not have any Pi bonds; therefore, it cannot
stabilize its radical.
Overall, the analysis done in the first part of the laboratory experiment suggested that
although the product, 4-(Bromomethyl) benzoic acid, was not completely pure, it was
still synthesized. The reaction did indeed work because of the results from NMR, and IR
analysis, percent yield, and qualitative measurement confirmed that it was satisfactorily
produced. The second part of the laboratory experiment heavily relied on a light source
to get the right rate of reaction, and rates were determined based on radical stability.
Correctly identifying the different hydrocarbons order and explaining why it is the case
was successfully done by completing the lab procedure and analyzing the results. Both
portions of the laboratory experiment shed light on bromination and radical stability as
they relate to organic mechanisms.