NITRATION OF METHYL BENZOATE

Mariellena P. Mendoza Human Biology 21 De La Salle University-Dasmarias Dasmarias City, Cavite,Philippines

ABSTRACT

Nitration is an introduction of nitrogen dioxide into a chemical compound. In the process, the methyl benzoate was nitrated to form a methyl m-nitro benzoate. The reagents were added very slowly to avoid vigorous reactions and the temperature was maintained low to avoid formation of di-nitro product. The percent yield was computed which give a result of 92.77 %. These shows how close the yield of the product to the original value. The melting point of the product was gathered with the use of melting point apparatus. This shows that the melting point of methyl m-nitro benzoate was 78 C which proved that it was a pure substance.

Introduction

The nitration of methyl benzoate is a typical electrophilic aromatic substitution reaction. The electrophile is the nitronium ion which is generated by the interaction of concentrated nitric and sulfuric acids. Figure 1 below shows the nitration of methyl benzoate and the nitronium ion generation.
H3C O H3C O

HNO3 CH4 H2SO 4 CH4

NO 2
+ +

HNO 3 + 2H 2 SO 4 Nitronium Ion

NO 2 + 2HSO 4 + H 3O

Figure 1: Nitration of Methyl Benzoate and Nitronium Ion Generation

The solvent which is the sulfuric acid, protonates the methyl benzoate in the structure above. The resonance stabilized arenium ion intermediate then transfers a proton to the basic bisulfate ion to give methyl 3-nitrobenzoate. The rate of formation of the Arenium ion, which is somewhat stabilized by ring resonance, determines the rate of reaction. The Carbomethoxy group is electron withdrawing, so it deactivates the ring relative to Benzene. The resultant resonance structures favor Meta substitution over Ortho/Para director [1].

Materials and Method

The conical flask was pre-weighed using the analytical balance then 20 drops of methyl benzoate was added inside the flask. The weight of the methyl benzoate was recorded. After addition, the conical flask with methyl benzoate was chilled in an ice bath together with the 2ml H2SO4 then swirled. After swirling, the nitrating agent was added in an ice bath then poured to the mixture slowly using the Pasteur pipette. If cloudiness will occur upon addition, just add few drops H2SO4 until the cloudiness disappear. Since, cloudiness did not occur we did not add anymore. The mixture was put in a water bath for 15 minutes. After waiting, 10g crushed ice was added to the mixture and stirred until melted. After solid product was formed, the vacuum filtration set-up was used to filter the mixture. The filtered product was washed with cold distilled water and 5% NaHCO3. The flask was emptied then the solid product was washed with cold distilled water then tested with blue litmus paper to know if its neutral. The watch glass was preweighed then transferred and dries over a steam bath. The weight of the dried product was determined. The percentage yield was computed and the melting point was obtained using the melting point apparatus. First, the dried product was scrape and grinded into fine powder. The product was transferred into a capillary tube and observed in the sample chamber. The remaining product was submitted to our instructor.

Results and Discussion

The percent yield of methyl m-nitro benzoate is shown in the table 1 below. This is to show how close the measured amount of the methyl m-nitro benzoate to the expected amount. Table 1: Percentage Yield of methyl m-nitro benzoate Mass of Methyl Benzoate 0.2868 g Mass of re-crystallized methyl m-nitro benzoate % Yield 0.2670 g 92.77%

The melting point of re-crystallized methyl m-nitro benzoate was 78 C with 0% difference. It was found with the use of melting point apparatus. The melting point proved that the product is a pure methyl m-nitro benzoate. The TLC Profile of the product was not founded because methyl m-nitro benzoate was a pure product. The mechanism for the synthesis of methyl m-nitro benzoate was shown in the Figure 2 below.

H O H N
+

O H SO 3H H

O N
+

SO 3H

H 2O

OH

OH

H3CO

H3CO

H3CO

H2SO4

O O2 N H
-

NO2 O SO3H

Figure 2: Mechanism for the synthesis of methyl m-nitro benzoate The reaction condition should be maintained at a very low temperature to avoid production of a dinitrated product. And the reagents are added very slowly to prevent vigorous reaction especially when acids are added.[2] Aside from methyl m-nitro benzoate, other product can also be formed. This can be Methyl-3,5-dinitrobenzoate because it is possible for methyl benzoate to nitrate twice. The figure below shows the nitration product that can be formed if phenyl benzoate is used.
O O O HNO3 H2SO 4 O O 2N O2 N

Figure 3: Nitration of Phenyl Benzoate

REFERENCES: [1] K. L. Williamson. Nitration of Methyl Benzoate, Macroscale and Microscale Organic Experiments, 2nd Ed. 1994. Houghton Mifflin, Boston [2] Pahlavan-Cherif. Experiment 3: Organic ChemistryII. Nitration. 2010. Retrieved from:swc2.hccs.edu/pahlavan/2425L3.pdf [3] Legaspi, G. A. and Sta. Ana, S.T. Essentials of Organic Chemistry Laboratory. 2010. Philippines. (Evaluation Copy)