Friedel Crafts

Friedel-Crafts Alkylation Reaction
Friedel-Crafts Alkylation Reaction Preparation of 1, 4-Di-t-butyl-2, 5-dimethoxybenzene Microscale Experiment Leah Monroe April 8, 2003
Organic Chemistry Lab II Experiment performed on March 20 and 25, 2003 Lab Partners (NMR only): Shannon Land and Jamie Yeadon
Abstract:
In this experiment, 1,4-dimethoxybenzene reacted with t-butyl alcohol to form 1, 4-Di-t-butyl-2, 5 dimethoxybenzene via a Friedel-Crafts Alkylation mechanism. A small amount of 1,4dimethoxybenzene was dissolved in acetic acid and t-butyl alcohol, along with H2SO4. The reaction was then allowed to go to completion at room temperature, and the crystals were washed with water and methanol. The percent yield of the product was 57.48%. This was lower due to the fact that many of the crystals were stuck in the reaction tube and could not be removed for weighing. Also, when a Pasteur pipet was used to remove the solvent from the reaction tube, many crystals were lost. The observed melting point of the product was 96 - 98C, which is considerably lower than the literature value of 104 105C. This may be due to impurities in the product or the sample may still have been wet. An NMR spectrum of the sample indicated that the sample was 1, 4-Di-t-butyl-2, 5 dimethoxybenzene and that the reaction was successful.
Friedel-Crafts Alkylation Reaction Introduction: The purpose of this experiment is to synthesize 1, 4-Di-t-butyl-2, 5 dimethoxybenzene by reacting 1, 4
dimethoxybenzene with tertiary-butyl alcohol in the presence of sulfuric acid as a Lewis acid catalyst. The reaction will occur via the Friedel-Crafts alkylation mechanism, and involves the attack of the aryl group at the electrophilic trimethylcarbocation. The resulting product will be recrystallized using methanol and characterized using IR spectroscopy and melting point analysis. Materials Used: 1 beaker, 400-mL ice for ice bath several Pasteur pipets, 1.0-mL glass stirring rod
Substances 1, 4dimethoxybenzene Formula Weight, g/mol
sand bath Erlenmeyer flask, 25-mL 10 x 100 mm reaction tube rubber bulb
Amount Used Moles Used Mole Ratio Melting Point C Boiling Point C Density g/mL
138.16 60 74.12 98.06 32.0 18.0 250.17
0.120 g 0.4 mL 200 L 2.0 mL 1.0 mL 2.5 mL product
8.69 x 10-4 N/A 0.00213 N/A N/A N/A product
1 to 1 N/A 2 to 1 N/A N/A N/A 1 to 1
58 - 60 N/A N/A N/A N/A N/A 104 - 105
N/A 118 83 327 64.7 212 N/A
1.053 1.049 0.7856 1.84 0.7914 1.0 N/A
Acetic acid t-butyl alcohol Concentrated H2SO4 Methanol Water

1, 4-Di-t-butyl-2, 5 dimethoxybenzene
Reaction and its Mechanism:

The limiting reagent for this reaction is 1, 4 dimethoxybenzene. See calculations section for explanation.
Overall Reaction: C8H10O2 + 2C4H10O

OCH3 CH3
C16H26O2 + 2H2O
OCH3 OH
CH3 CH3
H2SO4
+
OCH3
H2O
OCH3 1, 4-dimethoxybenzene
Tert-butyl alcohol
1,4-di-t-butyl-2,5-dimethoxybenzene
Mechanism:
CH3 CH3 CH3 OH
CH3
+
H
O
CH3 CH3 C+ CH3
SO3H
CH3 CH3
Sulfuric Acid
Friedel-Crafts Alkylation Reaction Mechanism (cont)

OCH3 CH3 CH3 C+ CH3 OCH3 OCH3 H
-
OSO3H H
OCH3 +
OCH3
OCH3 OCH3 H
OCH3
+ OCH3
OCH3 CH3 +C CH3 OCH3 OCH3 CH3 + OCH3 H
+ OCH3
OCH3
OCH3
+
-
H2SO4
OSO3H OCH3 +
OCH3 1,4-di-t-butyl-2,5-dimethoxybenzene
Procedure:
Dissolve 120 mg 1,4-dimethoxybenzene in a 10 x 100 mm reaction tube with 0.4 mL acetic acid. Add to it 0.2 mL t-butyl alcohol and heat gently until the mixture is in solution. Once its in solution, cool the mixture in ice. Then, add 0.4 mL concentrated H2SO4 (18 M) to the tube dropwise with a Pasteur pipet. After each drop is added, mix the solution thoroughly with a glass stirring rod. After all the H2SO4 has been added, remove the reaction tube from the ice and allow it to warm to room temperature. Allow the tube to remain at 20-25C for approximately 10 minutes in order to complete the reaction. Then cool the mixture in ice so that crystallization will occur. Very carefully, add a drop of water to the mixture. Stir with a glass stirring rod, then continue to add water dropwise with both cooling and mixing until 2.5 mL of water have been added to the reaction tube. Remove the solvent (liquid) layer using a glass Pasteur pipet with a
+ H OCH3 OCH3

rubber bulb on the end. Be sure to expel all the air out of the pipet before you lower it into the reaction mixture. Remove all the solvent from the cold solution. Now, add approximately 0.5 mL methanol to the reaction tube. Heat the tube until everything is in solution. Then, allow the tube to cool to room temperature. Once the tube is at room temperature, allow the tube to sit in ice until crystals form. If necessary, scratch the inside of the reaction tube with a glass stirring rod to induce crystallization. Once the crystals have formed, again, carefully, remove the solvent from the reaction tube with a glass Pasteur pipet and rubber bulb. Once most the solvent has been removed, place the reaction tube in a 25-mL Erlenmeyer flask, label it with your name, and place it under the fume hood for a few days. This will evaporate any left-over methanol. Then, weigh your product. Characterize it by taking a melting point. Also, take an NMR spectrum of the product. In order to prepare a sample for NMR, place approximately 40 mg of the sample in an NMR tube. Add 0.9 mL of carbon tetrachloride (CCL4). TMS is used as a reference to perform the NMR. Be sure to integrate your peaks after you perform the spectrum. Place all waste materials in their appropriate containers.
Data:
Mass 1,4-dimethoxybenzene used: 0.118 g Mass of product: 0.123 g Theoretical Yield: 0.214 g 1,4-di-t-butyl-2,5-dimethoxybenzene Percent Yield: 57.48% Observed melting point: 96 - 98C Literature value: 104 - 105C
Calculations:
Finding Limiting Reagent 1,4-dimethoxybenzene (DMOB) (0.118 g DMOB) (1 mol DMOB) (1 mol product) (250.17 g product) (138.16 g DMOB) (1 mol DMOB) (1 mol product) = 0.214 g product t-Butyl Alcohol (TBA) (0.2 mL TBA) (0.7856 g TBA) (1 mol TBA) (1 mol product) (250.17 g product) (1 mL TBA) (74.12 g TBA) (2 mol TBA) (1 mol product) = 0.265 g product The limiting reagent for this Friedel-Crafts alkylation reaction is 1,4-dimethoxybenzene. The 1,4-dimethoxybenzene yields less product than the t-Butyl Alcohol does, and therefore, the 1,4-dimethoxybenzene will be completely used up in the reaction and is the limiting reagent. Theoretical Yield 1,4-dimethoxybenzene (DMOB) (0.118 g DMOB) (1 mol DMOB) (1 mol product) (250.17 g product) (138.16 g DMOB) (1 mol DMOB) (1 mol product)
= 0.214 g product (1, 4-Di-t-butyl-2, 5 dimethoxybenzene)

Percent Yield For recrystallized product (mass of recrystallized product) (theoretical yield) (0.123 g) (0.214 g) x (100) = 57.48%
NMR Data and Interpretation:

My lab partners and I used one persons product and ran an NMR spectrum on it. We then analyzed the product, and that analysis indicated that the product was 1, 4-Di-t-butyl-2, 5 dimethoxybenzene as expected. A singlet at 6.7 ppm with 1 hydrogen indicated the presence of a hydrogen on a benzene ring. The singlet at 3.8 ppm with 3 hydrogens indicated a OCH3 group. The third singlet 1.3 ppm with 9 hydrogens was a tertiary butyl group. It consists of a central carbon with three methyl groups attached to it. When all these pieces were put together, the structure was that of 1, 4-Di-t-butyl-2, 5 dimethoxybenzene, the product obtained in the FriedelCrafts reaction performed in this experiment. Another singlet peak was also located downfield from the benzene ring peak at 6.7 ppm. This peak is due to the hydrogens on the aromatic ring.
Results and Conclusions:

In this experiment, 1,4-dimethoxybenzene reacted with t-butyl alcohol to form 1, 4-Di-t-butyl-2, 5 dimethoxybenzene via a Friedel-Crafts Alkylation mechanism. The percent yield of the product was 57.48%. This was lower due to the fact that many of the crystals were stuck in the reaction tube and could not be removed for weighing. In addition, when a Pasteur pipet was used to remove the solvent from the reaction tube, many crystals were lost. They stayed in the solvent and came up the Pasteur pipet, where they remained stuck and thus, were not weighed with the rest of the product. The observed melting point of the product was 96 - 98C, which is considerably lower than the literature value of 104 105C. This may be a result of the product still being wet when the melting point was taken. It may also be due to impurities in the product. Most likely, there is still some solvent present in the product that didnt evaporate. Although we let the product sit in a fume hood for a couple days, it was still in the reaction tube and may not have dried out completely before the melting point was taken. As a result, some of the solvent, even trace amounts of it, may still have been present in the product and this would have caused the observed melting point to be lower than the literature value, as was observed. An NMR spectrum of the sample indicated that the sample was 1, 4-Di-t-butyl-2, 5 dimethoxybenzene and that the reaction was successful. Please see the NMR Data and Interpretations section for a detailed interpretation of the spectrum. Overall, the Friedel-Crafts alkylation reaction and the experiment were successful.
Reference:
Class Handout. Taken from Williamsons manual, 2nd edition. D.C. Heath, p. 440 Weast, Robert C., ed. CRC Handbook of Chemistry and Physics. 70th ed. Boca Raton, FL: CRC Press, Inc., 1990.
Friedel-Crafts Alkylation Reaction Post-Lab Questions:

1. Please see above lab report for detailed mechanism, including resonance structures of the intermediates. 2. In place of t-butyl alcohol, one could use t-butyl chloride. However, this reaction is not convenient to do in the lab. You could also use 2-methylpropene. Both of these yield the same carbocations as the reaction that was performed in the experiment, and thus yield the same product when reacted with 1,4-dimethoxybenzene.
CH3 CH3 CH3 Cl H O SO3H CH3 CH3 C+ CH3
HCl
OSO3H
Sulfuric Acid
CH3 CH3 CH3 C CH2 H+ CH3 C+ CH3

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Friedel-Crafts Alkylation Reaction

138.16 60 74.12 98.06 32.0 18.0 250.17

0.120 g 0.4 mL 200 L 2.0 mL 1.0 mL 2.5 mL product

8.69 x 10-4 N/A 0.00213 N/A N/A N/A product

1 to 1 N/A 2 to 1 N/A N/A N/A 1 to 1

58 - 60 N/A N/A N/A N/A N/A 104 - 105

N/A 118 83 327 64.7 212 N/A

1.053 1.049 0.7856 1.84 0.7914 1.0 N/A

Acetic acid t-butyl alcohol Concentrated H2SO4 Methanol Water

Reaction and its Mechanism:

Overall Reaction: C8H10O2 + 2C4H10O

CH3 CH3 C+ CH3

Friedel-Crafts Alkylation Reaction Mechanism (cont)

Friedel-Crafts Alkylation Reaction

= 0.214 g product (1, 4-Di-t-butyl-2, 5 dimethoxybenzene)

Friedel-Crafts Alkylation Reaction

NMR Data and Interpretation:

Results and Conclusions:

Friedel-Crafts Alkylation Reaction Post-Lab Questions:

CH3 CH3 CH3 C CH2 H+ CH3 C+ CH3

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