FACULTY OF APPLIED SCIENCES

LABORATORY REPORT
FUNDAMENTAL ORGANIC CHEMISTRY
(CHM 457)
Title of Experiment Nitration of Methyl Benzoate
No. Experiment 5
Name of Student Norhidayu bt Adnan
Student ID Number 2021898286
Programme Code AS2532A
Date of Experiment is Done 20/05/2022
Date of Lab Report is Submitted 27/05/2022

Lecturer’s Name Dr Najmah bt P.S. Hassan

Title: Nitration of Methyl Benzoate

Objectives

i. To prepare methyl m-nitrobenzoate from methyl benzoate by nitration.

ii. To determine the percentage yield of the product.

Chemicals and Apparatus

Explain how you would load a sample into the capillary tube for the melting point experiment
with the help of a picture (you can insert a picture or sketch a picture).

1. Using a capillary tube that has been sealed at one end, the open end of the tube was
pressed into the sample.
2. The tube was inverted and tapped lightly on the benchtop to make sure the sample to
drop to the closed end.
3. The capillary tube closed end side was dropped a few times through a long narrow tube.
4. The height of loaded sample in the tube must be about 2 to 3mm to ensure accurate
result.

Results and Discussion

i. Identify nucleophile and electrophile from the experiment?

The nucleophile in this experiment is the benzene ring in methyl benzoate. While,
the electrophile is nitronium ion from the reaction between nitric acid sulphuric
acid.
 ii. Show the step-by-step of reactions mechanism on the formation of nitro
methyl benzoate from the reaction.

iii. As for the nitration experiment, the following parameters are being
used/observed

Amount of methylbenzoate used = 5.0 g

Volume of sulphuric and nitric acid used = excess
Isolated product yield = 3.5 g

a) Calculate the percent yield of the reaction

 1 𝑚𝑜𝑙 1 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑛𝑚𝑒𝑡ℎ𝑦𝑙𝑏𝑒𝑛𝑧𝑜𝑎𝑡𝑒 = 5.0 𝑔 × 136.15 𝑔 × 1 𝑚𝑜𝑙 𝑚𝑒𝑡ℎ𝑦𝑙 𝑏𝑒𝑛𝑧𝑜𝑎𝑡𝑒

= 0.0367 𝑚𝑜𝑙 𝑚𝑒𝑡ℎ𝑦𝑙 𝑚 − 𝑏𝑒𝑛𝑧𝑜𝑎𝑡𝑒

181.15 𝑔
𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 = 0.0367 𝑚𝑜𝑙 ×
1 𝑚𝑜𝑙
= 6.65 𝑔

3.5 𝑔
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑦𝑖𝑒𝑙𝑑 = × 100%
6.65 𝑔
= 52.6%

b) Explain why the isolated product yield is less than expected

The isolated product is less than expected might due to the sample not being
transferred thoroughly each time during the experiment. Also, there might be a
side reaction which compete with the wanted product.

iv. Explain briefly why the experiment was conducted at a very low
temperature of less than 0 °C

The reaction is exothermic. The temperature must be below 15˚C to

avoid dinitration. At higher temperature, formation of dinitration products would
increase. In this experiment, only one nitro group is wanted in the reaction.
Therefore, low temperature is required to avoid dinitration.

v. Explain why the final wash of the crystal product need to be tested with pH
paper.

To remove any acids left in the product thoroughly.

vi. Suggest a simple method to prove that the collected crystal is nitro methyl
benzoate.

By doing infrared (IR) spectroscopy or Thin Layer Chromatography (TLC).

Conclusion

In conclusion, methyl nitrobenzoate was prepared from the reaction between methyl benzoate
as nucleophile and nitronium ion as electrophile. Based on the results, the experimental mass
of the product is 6.65 g while the actual product yield is 3.5 g. The percentage yield of product
is calculated to be 52.6%. 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 literature melting point of methyl m-
nitrobenzoate is 76 to 80˚C. If the actual melting point of the product is a bit different than the
product, there might be errors while loading the sample into the capillary tube or there are
impurities in the final product that might affect the melting point.

References

1. Libretexts, & Nichols, L. (2021, March 5). 6.1D: Step-by-Step Procedures for Melting Point
Determination. Chemistry LibreTexts.
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Book%3A_Organic_Chemistry_
Lab_Techniques_(Nichols)/06%3A_Miscellaneous_Techniques/6.01%3A_Melting_Point/6.1
D%3A__Step-by-Step_Procedures_for_Melting_Point_Determination

2. Nitration of Methyl Benzoate - 904 Words | Education Index. (n.d.). EducationIndex.Com.

https://www.educationindex.com/essay/Nitration-of-Methyl-
BenzoatePKJWTTHEEY#:%7E:text=The%20amount%20of%20dinitration%20increases,tha
n%20the%20second%20NO2%20group.

3. 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
4. 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%20
less%20than,as%20during%20pouring%20or%20filtering.

Questions and Answers

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

The NO2 - group is a meta directing. The reaction happen at the meta position due to the ester
group in methyl benzoate being a meta deactivator and also, the ortho and para positions were
destabilized by adjacent positive changes on the resonance structure. Therefore, methyl
meta-nitrobenzoate is formed in this reaction.

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

This is because for the substitution of the second nitro group to the benzene ring to happen,
high activation energy is needed. When two NO2 groups were added to the ring, the activation
energy needed by the first NO2 group is lesser compared to the second NO2 group. Increasing
the temperature allows more energy for the second NO2 group to be added to the benzene ring.
Therefore, the amount of the dinitration increases when temperature is high. Otherwise, the
amount would be lower at low temperature.