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Chemical Engineering Program

CHEM 238
Experiment #4: Formal Lab Report
Electrophilic Aromatic Substitution- The Nitration of
Methyl Benzoate
Spring 2022

7/03/2022
“On my honor, as an Aggie, I have neither given nor received unauthorized aid on this academic
work.”
NAME Fatima Ahen
SIGNATURE
Table of Contents
INTRODUCTION .............................................................................................................................................................. 1
EXPERIMENTAL METHODS ................................................................................................................................................ 2
ANALYSIS AND CHARACTERIZATION .................................................................................................................................... 3
RESULTS & DISCUSSION ................................................................................................................................................... 3
CONCLUSION ................................................................................................................................................................. 6
REFERENCES .................................................................................................................................................................. 7
APPENDIX A: SAMPLE CALCULATIONS ................................................................................................................................ 8
APPENDIX B: SUPPORTING MATERIAL ................................................................................................................................ 9
Nitration of methyl benzoate to obtain methyl m-nitrobenzoate

Figure 1-shows the reaction between methyl benzoate and nitric acid in the presence of sulfuric acid to yield methyl-3-
nitrobenzoate.

Figure 2-shows the formation of nitronium ion by the protonation of nitric acid.

Figure 3- shows the intermediate from meta-attack and the final product methyl-3-nitrobenzoate.

Abstract
The objective of the experiment was to synthesize methyl nitrobenzoate from methyl benzoate,
concentrated nitric acid, and concentrated sulfuric acid to get methyl-3-nitrobenzoate. The process
included vacuum filtration, purification through recrystallization, and melting point determination.
Infrared radiation, Thin Line Chromatography, and Nuclear Magnetic Resonance were used to
characterize the compound obtained. The percentage yield of the methyl-3-nitrobenzoate was
calculated to be 48%.

Introduction
Nitration reaction that forms a resonance stabilized intermediate and is also an important
example of electrophilic substitution. The nitronium ion acts as an electrophile. That
intermediate later undergoes deprotonation to form an aromatic ring. A reaction between sulfuric
acid and methyl benzoate forms a protonated product, forming a meta product. The reaction is
considered an electrophilic substitution due to the displacement of hydrogen using 𝑁𝑂2 . Some of
the real life uses of methyl m-nitrobenzoate are in dyes and crop reducing agents as they act as

1
the starting materials.1 Methyl benzoate is used as a fragrant in the perfume industry and is also
food- grade safe compound, which means it can be used in food flavoring.2 The process of
nitration is also used to create explosives and pharmaceutical medicines.3 One of the significant
nitration disadvantages is the risk of explosions, this is because the nitrated products are highly
flammable.7 An advantage of nitration is that it can be further used to add nitrogen to a benzene
ring; this is useful as this can be taken further into substitution reactions.8

Experimental methods
The experiment in the lab started by filling a basin with ice. A vial containing an equimolar ratio
of the acid mixture sulfuric acid and nitric acid was placed inside the ice basin. Two vials, one
containing methyl benzoate and the other containing concentrated sulfuric acid, were also added
to the ice bath. Along with that, a flask was placed inside the ice bath. After leaving them inside
the ice bath for five minutes, a magnetic bar was placed in the Erlenmeyer flask, which was
placed on the stirring plate. A temperature probe was used. To that, 3.4 grams of methyl
benzoate was added, forming a colorless solution. At a time interval of three minutes, 5 mL of
the acid mixture was dropped using a Pasteur pipette into the vial. Yellow, brownish color was
observed. The mixture was left for ten minutes while it was stirring. The flask was then removed
from the ice bath and left to warm at room temperature for ten minutes.
Quenching then took place where the mixture was then poured into a beaker that contained ice
and left until all the ice melted. Cold vacuum filtration was done to obtain crystals. After that, a
small portion of crude product was placed in a vial. The rest was dissolved in 5 mL of methanol.
The hot stirring plate was turned on, and while using a water bath and temperature probe, the vial
that contained the crude product and methanol was gently swirled to dissolve all the crude
product. The temperature was made sure that it did not exceed the boiling point temperature. The
vial was placed in an ice bath. Methanol was used to rinse the Buchner, and cold vacuum
filtration was done. Cold methanol was also used to wash crystals.
A Pasteur pipette was used to transfer some of the mother liquor obtained in the vacuum flask to
a vial. The crystals were also transferred into a separate vial after ensuring they were dry. A
name label was placed on each vial, and the vials were placed in the cabinet under the hood for

2
further analysis next lab. In the next lab, H-NMR, melting point, Thin Line Chromatography,
and Infrared radiation was done to characterize the compound obtained and determine its purity.

Analysis and Characterization

Table 1- shows the strength, shape, and bond of methyl-3-nitrobenzoate obtained from the IR spectrum

Methyl-3-nitrobenzoate
Wavenumber (cm^-1) Strength Shape Bond
718 s narrow Meta disubstitution of benzene
3016 w narrow =C-H(aromatic)
1717 s narrow C=O
1526 s narrow C-C
1737 s narrow C-O
1350 s narrow N-O

Table 2- shows the initial mass of methyl-3-nitrobenzoate, the theoretical and final mass, and the percentage yield.

Compound Methyl m-nitrobenzoate

Theoretical mass (g) 4.526
Final mass (g) 2.175
Percentage Yield (%) 48%

Table 3- shows number of substances found in each compound and the calculated rf value of each substance obtained from TLC.

Compound Number of substances found Rf values

Methyl benzoate 2 0.73,0.79

Crude product 2 0.40,0.44

Mother liquor 3 0.19,0.36,0.5

Crystals 1 0.46

Isomeric mixture 3 0.36,0.47,0.54

Results & Discussion

The mechanism of the reaction starts by the benzene ring acting as a nucleophile by attacking the
nitrogen atom in the nitronium ion thus, leaving a positive charge on the benzene ring. From the
hydrogen that is bonded to the carbon next to the nitronium ion, the sulfuric acid removes that
hydrogen. Electrons shift from the hydrogen bond to the benzene ring. There are three different
locations on the benzene ring that the nitronium ion can be added to which are para, meta, and

3
ortho. In this reaction the meta product was the major product, this is because the carboxyl and
nitro groups are very strong electron-withdrawing groups. Also, with the use of methyl benzoate,
ortho and para intermediates have unstable energy intermediates. Electron withdrawing groups
prefer meta position and the reason is that the carbocation intermediate is a secondary
carbocation which has a greater stability compared to the ortho and para positions.

During the experiment, the reagents were placed inside an ice bath to prevent them from
evaporating as methanol evaporates at room temperature and to prevent the formation of methyl
benzoate. Additionally, ice bath was used to prevent the methyl-benzoate from over nitrating.
Initially, a colorless solution formed, this is because methyl benzoate dissolves in sulfuric acid.
Sulfuric acid is used to protonate the methyl benzoate and obtain a stable intermediate. The
reason why fuming gases were used in the reaction was to force a nitro group on the benzene
ring in order to obtain the meta product as the major product. To get the meta position as the
major product, vigorous conditions is required which includes the use of high temperatures and a
very strong of fuming nitric and sulfuric acid mixture. Sulfuric acid acted as a dehydrating agent
in this experiment and donated a proton to the nitric acid to help with the formation of the
nitronium ion.

A temperature probe was used to monitor the progress of the reaction and ensure that the
temperature does not rise which will cause in the formation of a dinitro product. The reagent was
added slowly to avoid a strong reaction. After the acid mixture was placed the reaction turned
into a milky yellow color. After all the crude product was dissolved an orange /yellow solution
was observed. The vial that contained the crude product and methanol was gently swirled to
dissolve all the crude product was placed in an ice bath to recrystallize the meta product. The
product on the Büchner funnel was rinsed with cold methanol to remove all the final soluble
impurities which would otherwise be left on the surface. Cold methanol was also used to wash
crystals because the obtained crystals do not dissolve in cold methanol.

The retention factor values are usually between 0 and 1. Ths smaller the rf value indicates that
the compound does not travel as fast as the solvent, the bigger the rf indicates the compound

4
travels as fast as the solvent. The compound with the highest rf value indicates that the
compound is least polar. The higher rf values as shown in table 4 shows that this is a non-polar
substance which is methyl benzoate. The other rf values were close to each other which is a
proof that those substances are more polar than methyl benzoate.

The resulting crystal weighed 2.174 g. A percent yield of 48% was then calculated. The
percentage yield obtained was very low indicating that much of the product was lost during the
experiment. Yield obtained can never be 100% and the reason that a low percentage yield is
obtained is because product was lost when transferring crystals from the Büchner funnel to the
vial. A mistake that occurred was losing one to two drops of the nitric acid and sulfuric acid
mixture when dropping the mixture into the flask. This could have potentially resulted to fewer
molecules on the nitronium reacting which in return resulted in a lower percentage yield. Also, a
small amount of the crystals was placed in a vial to be used for the TLC which effected the
percentage yield.

A melting point was then taken and determined to be 72.5-75.5 degrees Celsius. This is a broad
melting point indicating that the product obtained is impure and contains impurities. These
impurities can be water, methanol, or even reagent that has not reacted. Comparing to the
reference value of the melting point of 78 degrees Celsius it is clear that the melting point range
is broad and not sharp.

Infrared spectrum was done to characterize the functional groups in the compound. A stretching
was found at 718 𝑐𝑚−1indicating the presence of a meta disubstitution of benzene. Also, a
stretching is found at 3016 𝑐𝑚−1 indicating the presence of =C-H aromatic. The stretching at
1717 𝑐𝑚−1 indicates the presence of C=O. A stretching at 1350 𝑐𝑚−1 indicates the presence of
N-O. All these stretchings indicate that the product obtained is methyl-3-nitrobenzoate. Due to
the similarities between the standard infrared radiation spectrum and the infrared spectrum
obtained from the lab, it was verified that the compound obtained was the methyl-3-
nitrobenzoate.

5
Lastly, NMR was performed and five different integrated peaks were obtained indicating the
presence of five different protons with different environments. The H-NMR also verified that the
product obtained was not an ortho nor para but a meta product. The peak that had a chemical
shift of 3.93 ppm was a singlet, the peak with a chemical shift of 7.72 was a triplet which shows
that it has two surrounding neighboring hydrogens. The peak with a chemical shift 8.76 ppm is
the most deshielded and is a singlet. The peak at 8.25 ppm is a doublet. The peak located at 8.76
ppm and the peak located at 7.72 ppm both indicate that the major product obtained in the
reaction is the meta product. A peak at 1.79 ppm indicates the presence of water and the peak at
3.8 indicates the presence of methanol which are both impurities.

Conclusion
The product obtained was verified to be methyl-3-nitorbenzoate which is the meta position being
the major product. The reason meta product is major is due to the lower energy intermediate
formed. From the melting point it can be concluded that the product obtained is fairly impure due
to the broad melting point range 72.5-75.5 degrees Celsius. In order to improve the experiment
aromatic rings will be used to form major products such as ortho and para. Also, other techniques
such as mass spectrum and C-NMR can be used along with the other techniques to accurately
confirm the functional groups and further identify the compound. In order to improve the purity
of the product and obtain a purer product, separation losses and transferal losses should be
accounted for, and recording the mass of the compounds without loss of product to get a more
accurate percentage recovery. To get a percentage yield greater than the percentage yield
obtained which was 48%, the product will be handled with care and the transferral will occur
under the hood to prevent the air from causing any flying of the product, thus preventing
potential product loss.

6
References
Clement, B.; Harding, K. Organic Chemistry Experiments: Volume 1; Hayden- McNeil, 2020; p 97. Liu, X. Organic
Chemistry I; Kwantlen Polytechnic University, 2021; pp 210-220.
(1) Hackenberger; Ludwigshafen, A. Preparation of methyl m-nitrobenzoate, 1985.
(2) Morrison, W.; Larson, N.; Brabec, D.; Zhang, A. Methyl Benzoate As A Putative Alternative,
Environmentally Friendly Fumigant For The Control Of Stored Product Insects. Journal of Economic
Entomology 2019, 112 (5), 2458-2468.
(3) Hughes, A.; Glenn, I.; Patrick, A.; Ellington, A.; Anslyn, E. A Pattern Recognition Based Fluorescence
Quenching Assay For The Detection And Identification Of Nitrated Explosive Analytes. Chemistry - A
European Journal 2008, 14 (6), 1822-1827.
(4) ChemDraw JS Sample Page. https://chemdrawdirect.perkinelmer.cloud/js/sample/index.html
(accessed Mar 5, 2022).
(5) Speight, J. Environmental organic chemistry for engineers.
(7) Albright, L.; Carr, R.; Schmitt, R. Nitration: An Overview Of Recent Developments And Processes.
1996, 1-9.
(8) 18.4 Aromatic Nitration and Sulfonation.
https://chem.libretexts.org/Courses/University_of_Illinois_Springfield/UIS%3A_CHE_269_(Morsch_an
d_Andrews)/Chapters/Chapter_18%3A_Electrophilic_Aromatic_Substitution/18.04_Aromatic_Nitratio
n_and_Sulfonation (accessed Mar 5, 2022).

7
Appendix A: Sample Calculations

3.4𝑔
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑚𝑒𝑡ℎ𝑦𝑙 𝑏𝑒𝑛𝑧𝑜𝑎𝑡𝑒: = 0.0250 𝑚𝑜𝑙𝑒𝑠
136.16 𝑔/𝑚𝑜𝑙

𝑔
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑒𝑡ℎ𝑦𝑙 − 3 − 𝑛𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑜𝑎𝑡𝑒: 0.0250 𝑚𝑜𝑙𝑒𝑠 × 181.04 = 4.526 𝑔
𝑚𝑜𝑙

𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑦𝑖𝑒𝑙𝑑: 2.1745 𝑔

𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 2.1745 𝑔

% 𝑦𝑖𝑒𝑙𝑑 = × 100% = × 100% = 48%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 4.526 𝑔

𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑙𝑙𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 5.7

𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑖𝑛𝑔 𝑅𝑓 𝑣𝑎𝑙𝑢𝑒𝑠 ∶ = = 0.73
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑙𝑙𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 7.8

8
Appendix B: Supporting Material

Figure 4- Shows the H-NMR spectrum of methyl m-nitrobenzoate. Figure 5- shows the IR spectrum of methyl m-nitrobenzoate.

9
10
Introduction 2.5 points 2 points 1-1.25 points 0 points
(5)
Real World RWS is relevant to RWS is mentioned in RWS mentioned is No RWS
Significance the context of the a vague manner that completely mentioned
(2.5 pts) experiment and can somehow be irrelevant to the
explicitly provides related to the context of the
insight as to its real experiment. experiment.
world applications. (e.g. only a RWS of
(e.g. if synthesizing esters in general is
methyl benzoate, a included.)
general RWS of
esters is followed up
with the significance
of methyl benzoate
itself.)
2.5 points 2 points 1-1.25 points 0 points
Objective Objective is stated Objective is stated Objective stated is No objective
(2.5 pts) within the but is difficult to find partially incorrect or stated.
introduction and is within the text/ is incomplete.
clear and concise. objective is unclearly
written.

Procedure (5) 5 points 4 points 2 or 3 points 0-1 pts

Experimental methods Experimental Experimental Experimental
are methods are methods are methods
-Complete -Complete -Lack a few -Mostly
-Concise with only -Written in essential steps incomplete/lacks
the most important paragraph form required most of the
information (no extra -Not written in past -Written in essential steps
details that are not tense present tense of required
meaningful) -Goes into in an
-Written in past tense unnecessary detail instructional
-Written in paragraph of technical format
form techniques -Written as
steps (no
paragraph)

11
Results and 5 points 4 points 2 or 3 points 0-1 points
interpretation
(5)
All results are All results are All results are Some results are
presented with an presented with an presented; presented with
appropriate appropriate however, they incorrect
interpretation interpretation. are interpretation or
(e.g mass of product Interpretation is interpretated no interpretation
obtained AND mathematically incorrectly (e.g at all.
percentage incorrect for one or for a chemical
yield/recovery). more results. reaction
Interpretation of ALL calculating
results are correct and %recovery
are clearly presented instead of
(e.g using a table %yield).
format if applicable)

Spectra and 5 points 4 points 2-3 points 0-1 pts

analysis (5)
All spectral data is Some spectral data Some spectral No analysis is
presented neatly. is presented. data is there but present and/or
The spectra are not is presented only images of
present withing the Analysis unclearly or is the spectra are
body of the report, demonstrates some difficult to attached within
only a correct and understanding of follow. the main body
concise analysis is the relevance of the of the report
present. spectral data to the demonstrating
experiment. Analysis no
Analysis demonstrates understanding
demonstrates an the ability to of the
understanding of the read the spectra importance of
experiment (i.e but no attempt spectra.
differences in is made at
functional groups relating the
between reactant

12
 spectra and product data to the
spectra are clearly experiment.
demonstrated to
showcase the
confirmation of the
product.

Discussion (25)
2.5 pts 2 pts 1.25 pts 0-1 pts
Reaction The mechanism of The mechanism of Chemical Incorrect
mechanism the chemical the chemical reaction mechanism
(2.5 pts) reaction is presented reaction is mechanism is presented or no
clearly and presented but is presented but explanation or
correctly, only partially mostly presentation of
showcasing an correct and incorrect with reaction
understanding of the demonstrates little no mechanism
experiment. understanding of understanding seen.
the experiment. of the
experiment.
9-10 pts 7-8 pts 5-6 pts 0-2 pts
Justification of All decisions made Most decisions Few decisions Experimental
experimental during the made during the are justified decisions are
decisions (10 pts) experiment are experiment are correctly. justified
justified correctly. justified correctly. incorrectly or
(i.e. the addition of not justified.
certain
reagents/what was
their purpose?)

11.25-12.5 pts 8-10 pts 5-7 pts 0-5 pts

Justification of Experimental results -Experimental An attempt is Results are not
experimental are justified results are justified made at discussed
results (12.5 pts) thoroughly. (e.g. vaguely (e.g. low justifying the further than a
“low yield is due to yield is due to results, numerical
losses of reagents transfer losses) however, it is value. (E.g. the
during the

13
 experiment” and -An attempt is made only partially yield was 10%
sources of loss are at other correct. which is low.)
identified and justifications, -No alternative
suggestions are however they are justifications
made to further vague or only are seen.
improve the yield.) partially correct.
-Alternative
justifications are
also provided and
are mostly correct.

Conclusion (2.5) 2.5 points 2 points 1.5-1.25 points 1

-Conclusion -Conclusion -Conclusion -Little to no
accurately restates accurately restates restates the lab connection
the lab objective the lab objective objective but with the
and concisely and concisely does not objective is
indicates whether indicates whether indicate made.
the objective was the objective was whether it was
successfully successfully satisfied -Irrelevant
satisfied. satisfied. successfully, parts of the
experiment are
-The data collected -The data collected -Data collected highlighted.
is used to verify and is used to verify and is reiterated but
prove the concluded prove the concluded no attempt is -No
outcome. outcome. made at using it suggestions for
to verify the improvement
-Insightful -An attempt is made concluded are made.
explanations are at explaining outcome.
offered for unexpected
unexpected results/procedures. -No attempt is
results/procedures. made at
-Suggestions as to suggesting how
-Appropriate and how the experiment the experiment
relevant suggestions can be further can be
are made as to how improved are vague improved.

14
 the experiment can and/or do not apply
be further improved. in the context of the
experiment.

Presentation
(2.5 pts)
1.5 pts 1-1.25 pts 0.5-0.25 pts 0-0.1 pts
Structure, Report is well -Report is well -Report is -Report is
formatting, and organized and organized and somewhat difficult to
language (1.5 pts) cohesive and cohesive but organized with follow with
contains no contains 2-3 5-6 unexplained
mechanical errors. spelling or grammatical or tables/images.
Presentation seems grammatical errors. spelling errors. Contains 7 or
polished. more
grammatical or
spelling errors.
No attention to
detail is
evident.

1 pts 0.75-0.9 pts 0.5-0.6 pts 0 pts

References (1pts) References include References include References are No references
properly formatted properly formatted improperly are presented
citations with in-text citations but may be formatted (e.g. despite outer
citations. missing in-citations pasting a link material being
or vice versa. to a website) used in the
References are report (such as
obtained from References are References are in the RWS)
reliable sources obtained from obtained from
such as scientific reliable sources. unreliable This is
journals or reputable sources. plagiarism.
websites.

15
No blogs or dodgy
looking websites.

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