CHM457 FUNDAMENTAL ORGANIC CHEMISTRY

EXPERIMENT 5: Nitration of Methyl Benzoate

Name: Intan Nur Aida Syasya bt Johari (2022864668)

Group: As2531C
Group member’s:

Muhammad Ilyasa’ Bin Hazami 2022830194

Amir Nur Aiman Bin Amir Zahariman 2022475138

Zalila bt Zaharin 2022815076

NAME OF LECTURER: Dr. NAJMAH HASSAN
DATE OF SUBMISSION: 7th DECEMBER 2022

Allocated mark Mark

Aim/Objection of the
experiment
Introduction
Experimental Procedure
Results and Observations
Calculations
Discussions
Conclusions
Questions
References
TOTAL 30
DATE OF EXPERIMENT:30th NOVEMBER 2022
Objective

1. To prepare methyl m-nitrobenzoate from methyl benzoate nitration.

2. To determine the percentage-yield of product.

Introduction

Benzene rings are components of many important natural products and other useful organic
compounds. Therefore, the ability to put substituents on a benzene ring, at specific positions
relative to each other, is a very important factor in synthesizing many organic compounds.
The two main reaction types used for this are both substitutions: Electrophilic aromatic
Substitution (EAS) and Nucleophilic Aromatic Substitution (NAS). The benzene ring itself is
electron-rich, which make NAS difficult, unless there are a number of strongly electron-
withdrawing substituents on the ring. EAS, on the other hand, is a very useful method for
putting many different substituents on benzene ring, even if there are other substituents
already present. Organic Chemistry describes the factors involved in the region selectivity
for EAS reactions using benzene rings which already have substituents on them. In this
experiment, a nitro (-NO2) group put on a benzene ring which already has a n ester group
attached to it (methyl benzoate). The actual electrophile in the reaction is the nitronium ion
(NO2+), which is generate (in the reaction mixture) using concentrated nitric acid and
concentrated sulfuric acid. In this experiment a cool solution of the aromatic ester that has
been dissolved in sulfuric acid is reacted with a mixture of sulfuric acid and nitric acid. The
highly exothermic reaction is kept under control by cooling; then the mixture is poured onto
ice. The solid product is isolated by filtration and recrystallized from methanol in which it is
very soluble.

Materials

1. 8 mL of Conc. Sulphuric acid, H2SO4

2. 3.05 g Methyl Benzoate
3. 2 mL of Conc. Nitric acid, HNO3
4. 12 mL of cold water
5. 10 mL (2: 5 mL) of ice-cold Methanol
Apparatus

1. 100- & 250-mL Beaker

2. Thermometer
3. Analytical Balance
4. Ice-salt bath
5. Measuring cylinder
6. Pasteur pipet
7. 25 g Crushed ice
8. Heating mantle
9. Vacuum filtration setup
10. Glass watch
11. Filter paper
12. Melting point apparatus
13. Glass rod
14. Capillary tube
15. Bunsen burner.

Procedure

1. 1.6 mL of concentrated sulfuric acid is cooled to about 0 C in a 100-mL beaker

and 3.05 g of methyl benzoate was added.
2. The mixture was cooled to 0 C or below by using an ice-salt bath and a cool
mixture of 2 mL of concentrated sulfuric acid and 2 mL of concentrated nitric
acid were added very slowly using a Pasteur pipet.
3. The mixture was stirred continuously during the addition of the acids and the
temperature of the reaction was maintained below 15 C.
4. The mixture was warmed to room temperature after adding all of the acid.
5. The acid mixture was poured over 25 g of crushed ice in a 150-mL beaker after
15minutes.
6. The product was isolated by vacuum filtration through a Buchner funnel after the
ice has melted and it was washed with two 12-mL portions of cold water.
Then,two 5-mL portions of ice-cold methanol is used too to wash it too.
7. Weight the product
 8. Using a capillary tube that has been sealed at one end, the open end of the tube
was pressed into the sample.
9. The tube was inverted and tapped lightly on the benchtop to make sure the sample
to drop to the closed end.
10. The capillary tube closed end side was dropped a few times through a long
narrow tube.
11. The height of loaded sample in the tube must be about 2 to 3mm to ensure
accurate result.

Result and Observations

Mass of: (g)

Methyl Benzoate used 3.05
250 mL beaker 103.46
crushed ice 25
250 mL beaker + crushed ice 128.46
glass watch + filter paper 42.4321
glass watch + filter paper + crystal 42.9448
crystal obtained 0.5127

Melting point:

Starting melt: 74 ⁰C

Fully melt: 79 ⁰C

*Range: 74 ⁰C – 79 ⁰C*

Calculation

From experiment:

Methyl Benzoate = 136.15 g/mol, 3.05 g

Methyl 3-nitrobenzoate = 181.15 g/mol, X g

Crystal obtained (actual weigh) = 0.5127 g

Mol Methyl Benzoate

N= g/(g/mol) = 3.05g/136.15g/mol

=0.0224 mol

Hence, if 1 mol of Methyl Benzoate needed to produce 1 mol of Methyl 3-nitrobenzoate, then

0.0224 mol of Methyl Benzoate needed to produce 0.0224 mol of Methyl 3-nitrobenzoate.

Theoretical yield Methyl 3-nitrobenzoate

G=mol x g/mol = 0.0224 mol x 181.15 g/mol

=4.0578g

Percentage yield of product

%=Actual yield (g)/theoretical yield (g) x 100

=0.5127 g/4.0578 g x 100

=12.635%

Discussion

Nitrogen dioxide is added to an acidic chemical molecule during nitration.During the process,
methyl benzoate was nitrated to create methyl m-nitrobenzoate. The chemicals were injected
very gradually to avoid violent reactions and the temperature was kept as low as possible to
avoid the creation of dinotro product.The electrophilic aromatic replacements used in this
experiment serve as both the substituent and deposit a proton on an aromatic ring. When the
solvent sulfuric acid protonates the methyl benzoate, the resonance stabilised arenium ion
intermediate is generated.

Due to neighbouring positive charges on the resonance structure, the ortho and para sites
become unstable, which results in the reaction occurring at the meta position. The ester group
functions as a meta deactivator. Because the carboxyl and nitro groups are both potent
electron withdrawing groups, the meta product is the primary consequence.

The theoretical yield of methyl - 3-nitrobenzoate crude product is 4.0578 g, but the actual
yield is 0.5127 g. We receive a yield of 12.635% as a percentage. The melting point is
between 74 and 79 degrees Celsius, which is close to the 80 degrees Celsius.
Conclusion

In conclusion, from the reaction between methyl benzoate as nucleophile and nitronium ion
as electrophile, methyl nitrobenzoate was prepared. Based on the results, the actual yield was
0.5127 g as opposed to the 4.0578 g theoretical yield, giving us a percentage yield of
12.635%. We can infer that the substance we obtained is methyl m-nitrobenzoate because,
according to the physical constant provided, it melts at a temperature between 78 and 80
degrees Celsius.The percent product yield is less than expected because of the sample losses
while transferring the sample and might be due to side reactions occurring which compete
with the wanted reaction.The range of melting point of methyl m-nitrobenzoate is 74 to
79˚C.

Questions

1. Why is methyl m-nitrobenzoate formed in this reaction instead of the ortho or para isomer?

This is because methyl benzoate is an electron withdrawing unit (EWG) and a meta director.

2. Why does the amount of the dinitration increase at high temperature?

It is because of the decreasing of activation energy as the increasing of temperature.

3. Why is it important to add the nitric acid-sulphuric acid mixture slowly over a 15-minute
period?

It is because the reaction will generate a lot of heat, too much and it will affect the

yield of the product since it will form a by-product.

4. Indicate the product formed on nitration of each of the following compounds:

a) Benzene
b) toluene

c) Chlorobenzene

d) Benzoic acid
5. Write the full mechanism for the nitration of methyl benzoate
References

1. The Organic Chemistry Tutor. (2018, May 8). Nitration of MethylBenzoate and Nitration
of Bromobenzene [Video]. YouTube. https://www.youtube.com/watch?
v=eiRgQ0DLvu8&ab_channel=TheOrganicChemistryTutor
2. Theoretical yield - Calculating yields - OCR 21C - GCSE Chemistry (Single Science)
Revision - OCR 21st Century. (n.d.). BBC Bitesize.
https://www.bbc.co.uk/bitesize/guides/zqcjsrd/revision/1#:%7E:text=It%20is%20usually
%20less%20than,as%20during%20pouring%20or%20filtering
3. Nitration of Methyl Benzoate - 904 Words | Education Index. (n.d.).
EducationIndex.Com. https://www.educationindex.com/essay/Nitration-of-Methyl-
Benzoate-PKJWTTHEEY#:%7E:text=The%20amount%20of%20dinitration
%20increases,than%20the%20second%20NO2%20group