Experiment #2
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Feb 20, 2024
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Experiment #2: Synthesis of Benzoic Acid by Grignard Reaction
Objective:
Synthesize phenyl magnesium bromide, a Grignard reagent
Syntheses of benzoic acid and recrystallization of the product (benzoic acid) Reaction equation:
Materials:
Dry test tubes, bromobenzene, Mg metal, anhydrous ether, dry ice, glass rod, pH paper, needles, hexanes, NaOH, HCl, Mel-Temp apparatus. Reference Table:
Reagent
MM
Density
Safety Hazard
Structure
bromobenzene
157.01 g/mol
1.491 g/mL
Flammable, irritant, environmental hazard
NaOH
39.997 g/mol
1.515 g/mL
corrosive
HCl
36.46 g/mol
1.2 g/mL
Corrosive, acute toxic
Magnesium
24.305 g/mol
1.738 g/mL
Flammable
Anhydrous ether
74.12 g/mol
.706 g/mL
Flammable, irritant
Procedure:
1.
Mass balance and weigh paper to measure around 45-52 mg of prepared magnesium into one of the test tubes you received from your teaching assistant earlier. Record mass.
2.
In your fume hood, pipette about 0.5 mL of diethyl ether into test tube #1 and cap the tube with a rubber septum. Set this tube aside in your hood for now.
3.
In your fume hood, pipette 0.75 mL of diethyl ether into the second test tube in your fume hood and using the syringe from your glassware kit with needle provided by the teaching assistant, add 0.25 mL of bromobenzene to test tube
#2. Carefully push the needle through the middle of the rubber septum and inject the bromobenzene into the ether waiting there. Gently mix.
4.
Carefully in your fume hood, invert test tube #2 so that the syringe is underneath and test tube #2 is upside-down. Withdraw the contents of test tube #2 into the syringe by slowly pulling back the plunger while the tip of the needle is below the surface of the solution. Set the filled syringe on a clean paper towel in the fume hood. 5.
Remove the septum from test tube #1 and add approximately 0.1 mL of bromobenzene-diethyl ether solution from the syringe. Place the syringe back on the clean paper towel. 6.
Mix contents of test tube #1 with the glass rod and look for the generation of gas bubbles
7.
Using the dry glass stirring rod and grind the magnesium at the bottom of test tube #1. 8.
When gas bubbles appear, re-cap test tube #1 with the rubber septum and pierce it with a second needle. Make note of any heat changes 9.
Once bubbles in test tube #1 are observed and the tube re-capped, pierce the
septum of test tube #1 with the syringe and needle containing the bromobenzene-ether solution.
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10.
Slowly over a period of several minutes, add the remaining bromobenzene-
ether solution dropwise into test tube #1, then place test tube #1 in an ice bath until the rate slows. 11.
When all the bromobenzene-diethyl ether has been added, continue to monitor test tube #1 until the bubbling ceases and most of the magnesium metal (the limiting reagent) has been consumed in the reaction. 12.
Uncap the tube and start the reaction again by grinding if this is the case. Finally, check to see that the ether has not evaporated from test tube #1. This tube originally had 0.5 mL and 1.0 mL was added from the syringe. If test tube #1 contains less than 1 mL of volume, add more diethyl ether until there is 1.5 mL solution. Avoid any contact with water. 13.
In the fume hood, place a small piece of dry ice that has been dried thoroughly with a paper towel to remove condensation into a 30-50 mL beaker. Remove the vent needle from test tube #1 and withdraw its contents into the syringe as done before in this procedure
in part 1.
14.
Squirt this solution containing the in-situ Grignard reagent directly on the dry ice. 15.
Use a pipette to rinse test tube #1 with 1 mL of diethyl ether. 16.
Use the syringe and needle to transfer this rinse onto the dry ice also. Wait until all the dry ice sublimes before starting part 3.
17.
Prepare an ice bath in a 250 mL beaker and a hot water bath on the hot plate in a 100-150 mL beaker for Part 5 while waiting for the dry ice to sublime.
18.
Fill a test tube with deionized water and place it in the hot water bath. 19.
Add 1 mL of ethanol to a test tube and place it in the ice bath. 20.
Add 2 mL of 3 M hydrochloric acid to the 30-50 mL beaker containing the ether and benzoate salt. 21.
Stir and transfer the contents of the beaker to the glass centrifuge tube from the glassware kit. 22.
Rinse the beaker with 1 mL of diethyl ether and transfer that to the same centrifuge tube. 23.
Observe two separate layers in the centrifuge tube in part 3 and remove the aqueous layer from the bottom. Transfer this aqueous layer to a clean 10 mL Erlenmeyer flask. 24.
Add 1 mL of 3 M sodium hydroxide solution to the ether remaining in the centrifuge tube. Shake gently.
25.
Using a pipette remove the aqueous layer from the bottom of the centrifuge tube and transfer it to a clean 10 mL Erlenmeyer flask (not Flask #1). 26.
Wash the ether twice more with 0.5 mL of 3 M sodium hydroxide and transfer the aqueous layer on the bottom to the same flask.
27.
Add 1 mL of 3 M hydrochloric acid to Flask #2 and mix to protonate the sodium benzoate. 28.
Check the pH of the solution in Flask #2 with pH paper and continue adding the 3 M hydrochloric acid solution dropwise and mix until the contents of the flask are acidic.
29.
Cool Flask #2 in an ice bath for a few minutes. 30.
Use a Hirsch funnel and filter flask with the water aspirator in the fume hood to filter the contents of Flask #2 on the fritted funnel. Wash the benzoic acid with ice cold water while it is on the funnel. 31.
Allow the product to dry on the funnel for a few minutes. Save a small portion
of the benzoic acid product to be used for determination of the crude products
melting point. 32.
Use the glass stir rod to stir and mix as the boiling water is added. Leave the tube in the hot water bath as you mix. When all the benzoic acid has dissolved, remove the tube from the hot bath. Allow it to come to room temperature undisturbed and then place it in the ice bath for two minutes. 33.
Filter the contents of the tube using the Hirsch funnel and filter flask attached to the water aspirator. Use only ice-cold water to rinse any benzoic acid from the test tube
into the funnel.
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34.
Let the crystalline benzoic acid dry on the funnel for two minutes, then pipette 1-2 drops
of the ice-cold ethanol prepared at the end of Part 2 in this procedure over the crystals If moisture remains on the product, use a filter paper. 35.
Use the mass balance to measure the mass of your final benzoic acid. Record this in your lab.
Data:
Reagent/substance
Measurement
MP
magnesium
.051g
N/A
crude
.0456g
Started to melt at 87C. Melting point of 90C.
Observations:
While the grinding magnesium in test tube 1, it started to bubble and felt warm.
Bubbling appeared along with an orange-brown color when bromobenzene ether solution was added to tube #1.
Sodium benzoate was basic at first but was acidic after adding many drops of HCl. Percent yield:
Conclusion:
Overall, the Grignard reagent phenyl magnesium bromide and benzoic acid were synthesized. The Grignard reagent was formed by adding bromobenzene diethyl ether to magnesium. This mixture was added to dry ice to form benzoic acid. In the experiment, magnesium was our limiting reagent, and the reaction was successful. Because the Grignard reagent is a strong
nucleophile and base, it can easily react with water, so precautions included making sure all glassware was dried in an oven prior to starting the experiment.
Pre-lab questions: No prelab questions this week.
Post-lab questions:
1
. List the major by-products expected during this reaction and how to minimize them formation. What measurements or data can help understand formation of by-
product(s).
MgBr and Biphenyl
During this experiment, if there is acidic substance such as H+, MgBr(OH) will form a separate layer that will not dissolve in water.
References
National Center for Biotechnology Information. "PubChem Compound Summary for CID 7961, Bromobenzene"
PubChem
,
https://pubchem.ncbi.nlm.nih.gov/compound/Bro
mobenzene
. Accessed 15 February, 2022.
National Center for Biotechnology Information. "PubChem Compound Summary for CID 14798, Sodium hydroxide"
PubChem
,
https://pubchem.ncbi.nlm.nih.gov/compound/Sodium-
hydroxide
. Accessed 15 February, 2022.
National Center for Biotechnology Information. "PubChem Compound Summary for CID 313, Hydrochloric acid"
PubChem
,
https://pubchem.ncbi.nlm.nih.gov/compound/Hydrochloric-
acid
. Accessed 15 February, 2022.
Your preview ends here
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National Center for Biotechnology Information. "PubChem Compound Summary for CID 313, Hydrochloric acid"
PubChem
,
https://pubchem.ncbi.nlm.nih.gov/compound/Hydrochloric-
acid
. Accessed 15 February, 2022.
National Center for Biotechnology Information. "PubChem Compound Summary for CID 3283, Ether"
PubChem
,
https://pubchem.ncbi.nlm.nih.gov/compound/Ether
. Accessed 15 February, 2022.
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