I.

INTRODUCTION

Unlike alkenes, aromatics do not generally undergo addition reactions, instead the addition of
electrophiles result in a substitution reaction instead, which are greatly facilitated by addition of
a Lewis acid catalyst (Ashenhurst 2017); this substitution reaction is known as electrophilic
aromatic substitution (EAS), a reaction in which an electrophile substitutes a hydrogen atom in
an aromatic compound (Hardinger 2016). Generally, the form of this equation is given by
Equation 9.1., wherein Ar-H is an aromatic compound and E+ is any electrophile that can replace
H.

EQN 9.1.

In a more detailed manner, the mechanism for EAS can be seen in the following diagram, Figure
9.1.

FIGURE 9.1. Outline of mechanism for EAS.

In most EAS reactions, the rate of substitution is first order both in the aromatic compound as
well as the electrophile, the rate law of which can be seen in Equation 9.2.

EQN 9.2.

The reaction of a substituted ring with an activating group is faster than benzene; conversely, a
substituted ring with a deactivated group is slower than benzene (Alawwad 2015). Activated
substituents donate electrons, examples being OH-, NH2- and Me-, while deactivating
substituents withdraw electrons, examples being CF3-, NO2-, CN-, F-, Cl-, Br-, and I- (Carey 2006).
Thus, due to the presence of a carboxylic acid in the benzene ring, the reaction of benzoic acid
will be faster than that of benzene.

In this exercise, nitric acid will be protonated by sulfuric acid, forming a nitronium ion and
causing the loss of a water molecule, following the first step seen in Figure 9.1. The overall
second-order nature of the reaction is exhibited by the slow step or rate-determining step seen
in the second step of Figure 9.1., wherein two molecules to give a resonance stablilized
intermediate, the benzenonium ion. After retrieving the product, chemical tests will be utilized
to compare the starting material and product, such as Baeyer's test and reaction with bromine in
DCM to test for unsaturation, and reaction with ferrous hydroxide (Fe(OH)2) to test for the
presence of a nitro group where a positive test is the formation of the red-brown precipitate of
ferric hydroxide (see Equation 9.3.) (Mohrig, Hammond and Schatz 2010).

EQN 9.3.

The overall mechanism for the preparation of m-nitrobenzoic acid from benzoic acid can be seen
in Equation 9.4.

EQN 9.4.
Two side reactions may also possibly occur alongside the formation m-nitrobenzoic acid, and
these are: dinitration to form 3,5 - dinitrobenzoic acid (see Equation 9.5.) and sulfonation to
form m-carboxysulfonic acid (see Equation 9.6.). These side reactions, however, are not favored
and therefore will not take priority over the nitration itself.

EQN 9.5.

Dinitration to form 3,5 - dinitrobenzoic acid will not occur because benzoic acid is more reactive
than m-nitrobenzoic acid, and also because the presence of the ice bath ensures that the
temperature will not reach high enough to cause this reaction to occur (Shrestha 2010).

EQN 9.6.

Similarly, sulfonation to form m-carboxysulfonic acid will also not occur because of the presence
of the ice bath, ensuring the temperature is kept low and unable to catalyze the reaction, and
also because the reaction is not left to stand (Shrestha 2010). The formed NO2 is also
considerably more electrophilic than SO3.

VI. Discussion

Electrophilic aromatic substitution (EAS) is a reaction in which an electrophile substitutes a

hydrogen atom in an aromatic compound (Hardinger 2016), with the general reaction seen in
Equation 9.1. Aromatic hydrocarbons favor substitution over electrophilic addition; this is due to
the face that the nucleophile attacks the electrophile to form a distinctly non-aromatic substance
(such as cyclohexadiene derivatives) in addition reactions, while in substitution reactions the
nucleophile serves as a base and deprotonates an sp3-carbon to reform the double bond and
restore aromaticity (Carey 2006).

In this exercise, benzoic acid is the aromatic group that becomes substituted with a nitro group
via the nitronium ion to form m-nitrobenzoic acid.

To start, nitric acid is treated with sulfuric acid (a stronger acid) as a catalyst through an acid-
base reaction in an ice bath, wherein nitric acid acts as a base and releases the hydroxyl ion to
form the nitronium ion and water (see Equation 9.7.). NO2^+ is considerably more electrophilic
than SO3 due to the positive charge on the nitrogen atom due to ionization of the unpaired
electrons while SO3 has no charge, thus protonation would increase its electrophilicity (through
the partial positive charge on sulfur in HSO3+) (Burrows et al. 2017).

EQN 9.7.

Afterwards, this solution containing the nitronium ion is slowly added, dropwise, to a solution of
benzoic acid dissolved in sulfuric acid (done in order to deprotonate and later catalyze the EAS
reaction), with the receiver for the mixture is kept in an ice bath to ensure the temperature is
maintained between 0 and 10degC due to the highly exothermic reaction. This is also important
because unless the temperature is kept for low throughout the reaction some ortho product
may also be formed along the meta; carboxylic acid is a meta-director and promotes a
deactivated ring by the inductive effect (which transmits electronegativity throughout the pi
system) despite the presence of the nitro group (a strong activator), therefore the meta
positioning should be theoretically favored (see Equation 9.8.), however in reality, some ortho
positioning may also occur due to the presence of the nitro group unless the temperature is kept
cold (Truman State University 2017). The presence of deactivating groups, such as carboxylic
acid, causes a less reactive ring which results in a decreasing rate of reaction, therefore any
reaction with a deactivated aromatic ring would be slower than that of benzene, while the
opposite happens with activated aromatic rings (Smith 2008).

EQN 9.8.

Afterwards, the solution is left to stand at room temperature, then crushed ice is added for
formation of precipitate and the mixture is left to stand again; this is followed by filtration by
suction to collect the residue. The residue, which is the crude product, was recrystallized with
hot water to obtain a slightly yellow solid, presumably m-nitrobenzoic acid, with a percentage
yield of 34.8 (see Table 9.1.). The product endured losses due to the greatly acidic solution
damaging the filter paper during suction filtration prior to the recrystallization process, causing
the filtration to be done thrice in order to properly retrieve all solids; thus, the weights of the
individual filter papers had to be subtracted from the weighed recrystallized product. This may
also be the reason for the 135 degC melting point determined by oil bath (see Table 9.1.), as
there may have still been the presence of sulfuric acid or other impurities, such as particles of
the filter paper, in the recrystallized product.

Characterization was then undergone to differentiate the recrystallized product and the starting
material, benzoic acid. In regards to Baeyer's test and the reaction with bromine test, both
benzoic acid and recrystallized product showed no signs of reaction with the reagents (see Table
9.2.1.). In the reaction with ferrous hydroxide, however, there was a distinctive difference
between benzoic acid and the recrystallized product (see Table 9.2.2.).

In halogenation, aromatic groups will only react with a halogen in the presence of an Lewis acid
catalyst (such as FeBr3 for Br2 or FeCl3 for Cl2), in order to give the aryl halides chlorobenzene or
bromobenzene (see Equation 9.9.); however analogous reactions with I2 and F2 are not
synthetically useful because I2 is too unreactive and F2 reacts too violently (Smith 2008). Thus,
as the bromine in this exercise was in a dichloromethane solvent, there was no reaction with
either substance (see Table 9.2.1).

EQN 9.9.

In Baeyer's test, unlike alkenes, aromatic groups are stabilized by the delocalized pi electrons,
therefore it does not react as an alkene does. Therefore, where Baeyer's reagent would react
with an alkene, there is no reaction, and this is followed by benzoic acid and the recrystallized
product (similar to how m-nitrobenzoic acid would react) (see Table 9.2.1.).
Finally, the reaction with ferrous hydroxide was done to detect the presence of a nitro group,
which should be present in order to determine whether or not the recrystallized product has
NO2 present as m-nitrobenzoic acid does. As the nitro group is required in order to oxidize the
ferrous ion to the ferric ion in order to form the red-brown ferric hydroxide (Fe(OH)3) precipitate
(reaction seen in Equation 9.3.). An inert gas, from that used for the ignition of a Bunsen burner,
was passed into the test tube containing ferrous sulfate along with the substance to be tested in
order to displace the oxygen before any alcoholic potassium hydroxide (etKOH) was added, as
ferrous hydroxide would activate any oxygen present and favor such reaction over that of the
nitro group (Baudisch and Welo 1925); it is only after the oxygen has been properly displaced
from within the test tube that the etKOH was added, to ensure no accidental reaction of the
ferrous hydroxide with any remaining oxygen. Benzoic acid showed no reaction due to the lack of
a nitro group, while the recrystallized product, as m-nitrobenzoic acid would have, gave a
positive reaction through the formation of a brown precipitate (see Table 9.2.2.).

While the characterization tests lean in favor of the recrystallized product being m-nitrobenzoic
acid, the determined melting point suggests that there are still impurities present, and that the
obtained product cannot definitively be said to be m-nitrobenzoic acid and thus requires further
testing.

Nitration can be done several times to an aromatic ring, in order to increase addition of nitro
groups in para, ortho, and meta positions. For example, nitration can be done thrice on a sample
of toluene in order to yield trinitrotoluene (TNT), as seen in Equation 9.10.

9.10.

VII. References

A. Books

BURROWS A., HOLMAN J., PARSONS A., PILLING G., PRICE G. 2017. Chemistry^3: Introducing
Inorganic, Organic and Physical Chemistry. 3rd Edition. Oxford, UK: Oxford University Press.

CAREY F.A. 2006. Organic Chemistry. 6th Edition. New York, USA: McGraw-Hill Education.

MOHRIG J.R., HAMMOND C.N., SCHATZ P.F. 2010. Techniques in Organic Chemistry. 3rd Edition.
New York, USA: W.H. Freeman and Company.
SMITH J.G. 2008. Organic Chemistry. 2nd Edition. New York, USA: McGraw-Hill Education.

B. Journals

BAUDISCH O., WELO L.A. 1925. Journal of Biological Chemistry 1925(64): 753-770.

C. Web Sources

ALAWWAD L. 2015. Substitution Reactions of Benzene Derivatives. Retrieved November 8, 2017,

from:
https://chem.libretexts.org/Core/Organic_Chemistry/Arenes/Reactivity_of_Arenes/Substitution
_Reactions_of_Benzene_Derivatives

ASHENHURST J. 2017. Electrophilic Aromatic Substitution. Retrieved November 8, 2017, from:

https://www.masterorganicchemistry.com/2017/07/11/electrophilic-aromatic-substitution-
introduction/

HARDINGER S. 2016. Electrophilic Aromatic Substitution. Retrieved November 8, 2017, from:

http://www.chem.ucla.edu/~harding/notes/notes_14D_EAS02.pdf

SHRESTHA B. 2010. Electrophilic substitution reactions of benzene. Retrieved November 8, 2017,

from: http://chem-guide.blogspot.com/2010/04/electrophilic-substitution-reactions-of.html

TRUMAN STATE UNIVERSITY. 2017. Nitration of Benzoic Acid to Produce Methyl 3-Nitrobenzoate.
Retrieved November 18, 2017, from: http://chemlab.truman.edu/files/2015/07/Multi-2-
Nitration-of-Benzoic-Acid-2017.pdf