Scribd
Upload
3K views

Experiment 6: Nitration of Methyl Benzoate (Electrophilic Aromatic Substitution)

This experiment involves the nitration of methyl benzoate through electrophilic aromatic substitution. Methyl benzoate is reacted with nitric acid and sulfuric acid to produce methyl m-nitrobenzoate. The ester group of methyl benzoate deactivates the aromatic ring and directs the nitronium ion to the meta position. The product was recrystallized and had a melting point and percentage yield consistent with methyl m-nitrobenzoate. Maintaining the proper temperature range during addition of the reactants affected the percentage yield.

Uploaded by

Noor Azizah Zakaria
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
3K views

Experiment 6: Nitration of Methyl Benzoate (Electrophilic Aromatic Substitution)

This experiment involves the nitration of methyl benzoate through electrophilic aromatic substitution. Methyl benzoate is reacted with nitric acid and sulfuric acid to produce methyl m-nitrobenzoate. The ester group of methyl benzoate deactivates the aromatic ring and directs the nitronium ion to the meta position. The product was recrystallized and had a melting point and percentage yield consistent with methyl m-nitrobenzoate. Maintaining the proper temperature range during addition of the reactants affected the percentage yield.

Uploaded by

Noor Azizah Zakaria
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
You are on page 1/ 5

EXPERIMENT 6 : NITRATION OF METHYL BENZOATE (ELECTROPHILIC AROMATIC SUBSTITUTION)

OBJECTIVE To synthesize methyl nitrobenzene from methyl benzoate, concentrated nitric acid, and concentrated sulfuric acid via an electrophilic aromatic substitution reaction. INTRODUCTION

This reaction is a typical example of "Electrophilic Aromatic Substitution". The use of a mixture of Sulfuric Acid and Nitric Acid is the "classic" way to make the Nitronium Ion (NO2+).
2 H2SO4 + HNO3 NO2+ + H3O+ + 2 HSO4

This "Electrophile", the Nitronium Ion, is the active species that attacks the electron-rich aromatic ring in the first step of the mechanism of this reaction. If the aromatic ring contains electron donating groups like hydroxyl (OH) , or alkoxy (OR) groups, the reaction is very rapid, and often more than one nitro group will become attached to the aromatic ring.In the example we will use in this laboratory exercise, the ring substituent, the ester group (CO2R), is electron withdrawing. This substituent slows the attack of the electrophile and allows isolation of a monosubstituted product.

PROCEDURE 1. 6 ml of concentrated sulfuric acid was added to a 100 ml beaker and cooled in an ice bath for 5-10 minutes. 2. 3.05 g of methyl benzoate was added to the cold sulfuric acid. 3. Left in ice bath for additional 5 minutes after the addition. 4. 2 ml of concentrated sulfuric acid was added to 2 ml concentrated nitric acid in order to prepare H2SO4/HNO3 mixture. 5. The mixture was cooled in an ice bath.

6. By using Pasteur pipet, H2SO4/HNO3 mixture was added slowly to the H2SO4/ methylbenzoate mixture. 7. The mixture was swirled after every drop was added. 8. The reaction flask was kept in ice bath during the addition and the temperature was maintained in the range of 5-20 . 9. After the addition completed, the entire reaction mixture was left to warm to room temperature. 10. For completion, the reaction mixture was let to stand for an additional 15 minutes. 11. The entire mixture the poured onto about 25g of crushed ice. 12. Before proceed with vacuum filtration, all the ice must be completely melted. 13. The solid prodeuct was isolated by suction filtration using a Buchner funnel. 14. The solid product was washed with two 12 ml portions of cold water and followed by two 5 ml portion of ice cold methanol. 15. The crude product was recrystallized by using an equal weight of methanol as our recrystallization solvent. 16. The purified product was collected by vacuum filtration and washed with a little cold methanol. 17. The product was dried, weighed and the melting point was determined. 18. The melting point obtained was used to identify the isomer. RESULTS Mass (g) Watchglass 37.5446 Watchglass + product 40.6668 Product 3.1222 Table of weighing Percentage yield = 25% Melting point = 75-78

CALCULATION C8H8O2 + HNO3 C8H7NO4 + H20 Mass of methyl benzoate = density x volume = (1.094 g ml-1)(2.8 ml) = 3.0632 g

Mole of methyl benzoate = = 0.0225 mol Mass of nitric acid = (1.51 g ml-1)(2 ml) = 3.02 g Mole of nitric acid = = 0.0479 mol methyl benzoate is the limiting reactant 1 mole methyl benzoate produced 1 mole methyl m-nitrobenzoate

Theoretical mass of methyl m-nitrobenzoate = (0.0225 mol)(181.14 g mol-1) = 4.0757 g Actual mass of methyl m-nitrobenzoate = 3.1222 g Percentage yield = = = 77%

x 100% x 100%

DISCUSSION In this experiment, electrophilic aromatic substitutions involved the replacement of a proton on an aromatic ring with an electrophile that becomes a substituent. The solvent sulfuric acid protonates the methyl benzoate, creating the resonance stabilized arenium ion intermediate. The electron-deficient nitronium ion reacts with the protonated intermediate at the meta position. The ester group is a meta-deactivator, and the reaction takes place at the meta position because the ortho and para positions are destabilized by adjacent positive charges on the resonance structure. The major product is the meta product due to the carboxyl and nitro groups both being powerful electron withdrawing groups. After re-crystallization the product was massed to be 3.1222 g, which is a 77% yield. There was not that much change in the yield. The change in yield from the crude product to the re-crystallized product could mean that the product was either impure, or some product was lost in the process of re-crystallization. The melting point of the re-crystallized product was measured between 75C and 78C, which is very close to the reported literature value of 78C. The possibilities that cause our yield is not so good because we do not maintain the temperature in the range of 5-20 during the addition of H2SO4/HNO3 mixture into H2SO4/ methylbenzoate mixture. And some of the product might evaporate due to high temperature.

CONCLUSION The results show that methyl benzoate is the limiting reagent and Nitric Acid is the excess reagent. The theoretical yield of bromine was 4.0757 g. The percent yield of the chemical reaction yield was 77%. The result also shows that the product after re-crystallization was 3.1222 g.

QUESTION 1. Methyl m-Nitrobenzoate is formed in this reaction rather that ortho/para isomers because of the ester group of the starting product of methylbenzoate. The functional group of ester is an electron withdrawing group causing nitrobenzene (NO2) to become in the meta position. Thus NO2 is a deactivating group causing itself to be a meta director.

2. Structure of product Benzene Toluene

Chlorobenzene

Benzoic acid

3. Mechanism for nitration of methyl benzoate

CO2Me H H
methyl benzoate

NO2+

slow
Step 1

CO2Me H H NO2

CO2Me fast
Step 2

NO2

carbocation intermediate

methyl m-nitrobenzoate

REFERENCES 1. CRC, Handbook of Chemistry and Physics, 75th Ed., 1994/95, editor D. Lide, Cleveland, OH: CRC Press, p. C-965, #6007. 2. The Merck Index, 10th Ed., 1983, editor M. Windholz, Rathway, N.J.: Merck&Co., Inc., p. 933, #6357. 3. http://www.allfreepapers.com/print/Nitration-Methyl-Benzoate/2209.html

You might also like