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Nitrating Methyl Benzoate: Electrophilic Aromatic Substitution Nitrating Methyl Benzoate: Electrophilic Aromatic Substitution Leah Monroe March

25, 2003

Organic Chemistry Lab II Experiment performed on March 13 and 18, 2003

Abstract: The purpose of this experiment was to synthesize methyl nitrobenzoate from methyl benzoate,
concentrated HNO3, and concentrated H2SO4 via an electrophilic aromatic substitution reaction. The HNO3 and H2SO4 were combined to form a nitrating solution, which was mixed with a mixture of methyl benzoate and H2SO4. The resulting mixture sat in an ice-water bath for 40 minutes, then had 10 mL chilled water added to it. The solution was then allowed to sit for an additional 10 minutes to complete crystal formation. The crystals were then collected using vacuum filtration. The product was isolated and recrystallized using 95% ethanol. Following recrystallization, melting point and infrared spectrum were used to identify and characterize the product of the reaction. The percent recovery of this reaction for the recrystallized product was 56.42%. Percent yield for the crude product and percent recovery following recrystallization were not calculated because the written procedure from the reference did not require it. Melting point and infrared spectroscopy analyses indicated the product was indeed methyl m-nitrobenzoate and that the reaction was successful.

Nitrating Methyl Benzoate: Electrophilic Aromatic Substitution Introduction: The purpose of this experiment is to synthesize methyl nitrobenzoate from methyl benzoate,
concentrated HNO3, and concentrated H2SO4 via an electrophilic aromatic substitution reaction. The product will then be isolated and recrystallized using 95% ethanol. Following recrystallization, melting point and infrared spectrum will be used to identify and characterize the product of the reaction. Regiochemistry of the product will also be determined.

Materials Used:
50-mL beaker 400-mL beaker Hirsch funnel with tubing 25-mL Erlenmeyer flask 125-mL Erlenmeyer flask glass stirring rod 10-mL graduated cylinder utility clamp 50-mL graduated cylinder marking pen microspatula 3 Pasteur pipets, with latex bulb 3 pipets, 1-mL, with rubber bulb sand bath support stand 2 test tubes, 15 x 125-mm

Reagents and Properties:


Substances
Formula Weight

g/mol

Quantity

Methyl benzoate Methyl nitrobenzoate Conc. Nitric acid Conc. sulfuric acid Ethanol, 95%

136.15 181.13 63.01 98.08 46.07

0.55 g product 0.5 mL 1.6 mL 2-3 mL

4.039 x 10-3 N/A 1.192 x 10-2 3.0 x 10-2 N/A

Moles Used Mole Ratio Melting Point C

Boiling Point C

Density

1 to 1 1 to 1 N/A N/A N/A

113 115 78 80 N/A N/A N/A

N/A N/A 121 N/A N/A

N/A N/A 1.5027 g/mL 1.841 g/mL N/A

Reaction and its Mechanism: Overall Reaction:


O C OCH3
O

HNO3 H2SO4
NO2

OCH3

H2O

H2SO4

Methyl benzoate

Methyl m-nitrobenzoate

Nitrating Methyl Benzoate: Electrophilic Aromatic Substitution Mechanism:


H .. O N .. O .. O.. + H O SO3H H H
+

O .. O.. +
-

O N

SO3H

O N O +

H2O

Nitric Acid

Sulfuric Acid

O C OCH3

O C OCH3

O C OCH3 + H2SO4

+
O N O
+

NO2 H
-

NO2 O SO3H Methyl m-nitrobenzoate

Procedure:
Part 1 Preparing the Ice-Water Bath and Chilled Water Place equal volumes of ice and tap water into a 400-mL beaker so that the beaker is approximately 75% full. Then, prepare chilled water for parts three and four of this experiment by pouring approximately 30 mL distilled or deionized water into a 125-mL Erlenmeyer flask. Place the flask into the ice-water bath. Part 2 Preparing the Nitrating Solution Label two 15 x 125-mm test tubes nitric acid and sulfuric acid, respectively. Transfer 0.5 mL concentrated nitric acid into the tube labeled nitric acid. Then, transfer 0.6 mL concentrated sulfuric acid into the tube labeled sulfuric acid. Chill both the test tubes with the acids in them in the ice-water bath for 15 minutes. Then, use a Pasteur pipet to very slowly add the cold sulfuric acid drop by drop into the cold nitric acid. Swirl the reaction mixture after every three drops are added. After adding all the sulfuric acid to the nitric acid, allow the nitrating solution to stand in the ice-water bath for 10 minutes. Part 3 Nitrating Methyl Benzoate Place approximately 0.55 g methyl benzoate into a 25-mL Erlenmeyer flask and add 1.0 mL concentrated sulfuric acid. Clamp the flask containing the mixture to a support stand. Lower the flask into the ice-water bath for 5 minutes, being sure to prevent the bath water from entering the reaction flask. After the 5 minutes are up, use a Pasteur pipet to slowly add the nitrating solution in the test tube to the Erlenmeyer flask containing the methyl benzoate and sulfuric acid. After all the nitrating solution has been added, allow the mixture to stand in the ice-water bath for 30-45 minutes. Make sure you swirl the flask every 5 minutes. After the 30-45 minutes are up, add 10 mL chilled water to a 50-mL beaker. Slowly and carefully add the cold reaction mixture, with stirring, to the chilled water. Then, allow the chilled solution to stand 5-10 minutes to complete crystal formation. Part 4 Isolating, Purifying, and Characterizing the Product Filter the reaction mixture via vacuum filtration. Wash the crystals with approximately 10 m L of chilled water in order to remove any residual acid. Then, allow your product to air dry in the filter tunnel for 10 minutes. Then, put your product crystals into a 10-mL Erlenmeyer flask and add 1 mL of 95% ethanol. Swirl the flask to mix. Heat the flask in a sand bath until the crystals are in solution and the solution boils. Boil the solution for a couple minutes, then remove the flask from the sand bath and allow it to cool to room temperature. Add approximately 0.5 mL ice-cold ethanol to the flask and swirl to loosen the crystals. Then filter the crystals using vacuum filtration. Allow the product to dry in the filter funnel for a couple days. Then, weigh your product and record its mass.

Nitrating Methyl Benzoate: Electrophilic Aromatic Substitution


Part 5 Melting Points and Infrared Spectrum Prepare a melting point capillary of the recrystallized product and take its melting point. Also, perform an infrared spectrum on the recrystallized product. Do this by adding 100 mg KBR to approximately 1mg of the recrystallized product. Mix the two using a mortar and pestle, being sure to grind the two compounds into a fine powder. Place some of this mixture in a microcup, making sure the surface is smooth. Then place the pellet in the infrared spectrometer and obtain an infrared spectrum of the product. Part 5 Clean Up Place all waste materials in their appropriate waste containers.

Data and Calculations:


Mass methyl benzoate used: 0.554 g Mass recrystallized crystals: 0.413 g Percent Yield: 56.42% Melting Point recrystallized product: 77.5 - 80C Literature Value: 78 - 80C Finding Limiting Reagent HNO3 (0.5 mL HNO3) (1.5027 g HNO3) (1 mol HNO3) (1 mol methyl nitrobenzoate) (181.3 g methyl nitrobenzoate) (1 mL HNO3) (63.01 g HNO3) (1 mol HNO3) (1 mol methyl nitrobenzoate)

= 2.159 g methyl nitrobenzoate H2SO4 (0.6 mL H2SO4) (1.841 g H2SO4) (1 mol H2SO4) (1 mol methyl nitrobenzoate) (181.3 g methyl nitrobenzoate) (1 mL H2SO4) (98.08 g H2SO4) (1 mol H2SO4) (1 mol methyl nitrobenzoate)

= 2.039 g methyl nitrobenzoate Methyl Benzoate (0.554 g methyl benzoate)


(1 mol methyl benzoate) (1 mol methyl nitrobenzoate) (181.13 g methyl nitrobenzoate)

(136.15 g methyl benzoate)

(1 mol methyl benzoate)

(1 mol methyl nitrobenzoate)

= 0.732 g methyl nitrobenzoate The limiting reagent for this electrophilic aromatic substitution reaction is methyl benzoate. It yields the least amount of methyl nitrobenzoate in this reaction, and therefore is the limiting reagent. Theoretical Yield (0.554 g methyl benzoate) (1 mol methyl benzoate) (1 mol methyl nitrobenzoate) (181.13 g methyl nitrobenzoate) (1 mol methyl nitrobenzoate) (136.15 g methyl benzoate) (1 mol methyl benzoate) = 0.732 g methyl nitrobenzoate Percent Yield For recrystallized product (mass of recrystallized methyl nitrobenzoate) (theoretical yield) =56.42% yield (0.413 g methyl nitrobenzoate) (0.732 g methyl nitrobenzoate) x (100) =

Nitrating Methyl Benzoate: Electrophilic Aromatic Substitution Observed Properties and IR Data and Interpretation:
An infrared spectrum of the recrystallized product revealed that it was methyl m-nitrobenzoate. The peak located at 1534.48 cm-1 indicates the presence of an NO2 group. The peak located at 1734.33 cm-1 is the result of a carbonyl group and the peak at 1584.9 cm-1 indicates the presence of a benzene ring. Also, the peak at 1076.30 cm-1 indicates a CO bond, which is present in methyl m-nitrobenzoate. Regarding the regiochemistry of the obtained product, the peak at 823.14 cm-1 indicated that the product was a meta-substituted benzene, as was predicted. All these peaks together indicate that the product was methyl m-nitrobenzoate.

Results and Conclusions:


The electrophilic aromatic substitution reaction between methyl benzoate and a nitrating solution of sulfuric and nitric acids was successful and yielded methyl m-nitrobenzoate. The percent yield of the recrystallized product was 56.42%. Percent yield of the crude product was not calculated because the experiment did not include this step and consequently, percent recovery for the recrystallized product cannot be calculated either. The melting point of the recrystallized product was 77.5 - 80C. This was then compared with a data table given in the experiment in order to determine the regiochemistry of the obtained product. The observed melting point was extremely close to the literature value of 78 - 80C for the meta-substituted product. Therefore, analysis of the melting point determined that the product was methyl meta-nitrobenzoate, as could be predicted. Since CO2H3 is a strongly deactivating group, it is meta-directing. Thus, we expected the NO2 group to be added to the methyl benzoate at the meta position. The melting point analysis proved that this is what happened and the product obtained was methyl mnitrobenzoate. An infrared spectrum of the product also confirmed its identity as methyl m-nitrobenzoate. A peak located at 1534.48 cm-1 indicated the presence of an NO2 group. The peak located at 1734.33 cm-1 was the result of a carbonyl group and the peak at 1584.9 cm-1 indicated the presence of a benzene ring. Another peak at 1076.30 cm-1 indicated a CO bond, which is present in methyl m-nitrobenzoate. Regarding the regiochemistry of the obtained product, the peak at 823.14 cm-1 indicated that the product was a meta-substituted benzene, as was predicted. All these peaks together indicated that the product was methyl m-nitrobenzoate.

Reference:
Chemistry Lab Experiments CHEM 224 REAC 716 pgs. 61 71 By Wigal/Manion/LeFevre/Wade, Jr./Rapp/Lee/Wikholm Weast, Robert C., ed. CRC Handbook of Chemistry and Physics. 70th ed. Boca Raton, FL: CRC Press, Inc., 1990.

Post-Lab Questions:
1. (a) The percent yield of my product was 56.42%. See Data section for calculation. (b) The melting point of my product was 77.5 - 80C. (c) The observed melting point of 77.5 - 80C was most closely related to the literature melting point of 78 80C for a meta substitututed product. Therefore, my product has a meta- regiochemistry. The metaproduct forms because the ortho- and para- products both have very unstable resonance forms with 2 positive charges next to each other. The two positive charges right next to one another cause the resonance forms to be unstable, so ortho- and para- substituted products do not form in this reaction. The meta- position is electron-rich, and thus reacts best with the NO2 group to form methyl m-nitrobenzoate. Also, we knew the meta- product was going to form because CO2H3 is a strongly deactivating group and is meta-directing. Thus, we expected the NO2 group to be added to the methyl benzoate at the meta position. This was confirmed by analyzing the melting point.

Nitrating Methyl Benzoate: Electrophilic Aromatic Substitution


(d) The structure of my product is:
O C OCH3

NO2 Methyl m-nitrobenzoate

2. The resonance forms for the arenium ion formed during this reaction are as follows:
O C OCH3 O C OCH3 O C OCH3

+
NO2 NO2

+
NO2

+
Methyl m-nitrobenzoate

3. The first nitration proceeds much faster than the second two because the first NO2 group to be added is added to the isolated toluene. The methyl group on the benzene ring is an activating group. It causes the benzene ring to be more electron rich and thus, have a high reactivity. CH3 is an ortho-para activator. So, the first NO2 group adds to the toluene in the para-position in order to avoid steric crowding from the methyl group. The toluene has now been converted to para- nitrotoluene. The NO2 group that is now on the benzene ring is a deactivating group, and causes the benzene ring to be not nearly as reactive as it was before the first NO2 group was added. Thus, the second and third nitrations occur much more slowly than does the first one.