Experiment #

Friedel-Crafts Acetylation of Biphenyl and Column Chromatography

Your Name
Lab Partner—(insert name)
Teaching Assistant—(insert name)
Date Performed—March 11, 2017
Date Due—March 18, 2017
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Experimental Objective
To synthesize 4-acetylbiphenyl through a Friedel-Crafts Acetylation of biphenyl and to
then purify the crude product through the usage of flash column chromatography. Further, to
characterize the product by way of thin layer chromatography, IR, and melting point analysis.

Reagents Used

Reaction Scheme

Figure 1. Acetylation of biphenyl via Friedel-Crafts Acetylation

Procedure
Acetylation Reaction and Work-up
A dry 25 mL round-bottom flask equipped with a magnetic stir bar was fitted with a
water-jacketed reflux condenser and a drying tube (with a granular CaCl₂ drying agent). This
setup was placed in a sand bath atop the hot-plate. The setup was secured by the ring-stand.
Methylene chloride (6 mL) was added to the flask, followed by anhydrous aluminum
chloride (0.456 g) and powder biphenyl (0.247 g). Care was taken to close the aluminum
chloride vial between massings to avoid the adsorption of moisture. The teaching assistant added
acetyl chloride (0.15 mL) to the flask in one portion.
The mixture was stirred for 3 minutes at room temperature, followed by heating to gentle
reflux for 10 minutes. After cooling to room temperature, the condenser and drying tube were
removed, and the flask was then placed in an ice bath for approximately 5 minutes.
The stir bar was removed and 3M HCl (3 mL) was added. The flask was capped, inverted
gently, and vented, and the contents were transferred to a test tube; the flask was rinsed with
methylene chloride (2 mL) and the rinsing was added to the test tube. The organic layer was
removed and placed in a second test tube. The aqueous layer in the first test tube was extracted
with methylene chloride (2 mL). The combined organic layers were then extracted with 1M
NaOH (3 mL). The organic layer was transferred to a third test tube where it was washed with
saturated aqueous NaCl (3 mL). The organic layer was removed, transferred to a 50 mL
Erlenmeyer flask, and dried over sodium sulfate.
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The dried solution was decanted into a clean 10 mL round-bottom flask and concentrated
under vacuum. A TLC was run in methylene chloride:ethyl acetate 19:1. The crude product was
spotted along with a biphenyl and acetyl chloride standard. The Rf values were calculated for any
significant spots.

Flash Column Chromatography

A fritted column was prepared to purify the crude product. The column was dry-packed with
approximately 2.5” of silica gel (70-230 mesh SiO2). The sides of the column were tapped gently
with a piece of rubber tubing to help tightly pack the stationary phase. The column was clamped
vertically and the stopcock was tightened. A 25 mL Erlenmeyer flask was placed below the
column. A 14/20 rubber septum and a 20 mL syringe were added when needed to generate
pressure.
The column was filled with hexanes (25 mL), which were pushed through the column using
the rubber septum and syringe. Once the silica was sufficiently wet with no cracks, a ~⅛” layer
of acid-washed Ottawa sand was placed atop the silica using a stemmed funnel. The crude
product was dissolved in methylene chloride (0.3 mL) and the product was wet loaded with a
glass pipette. The solution was pushed down gently with air pressure until the solution was
adsorbed on the silica and the sand was dry. A drop of the crude product was set aside for the
TLC plate.
The column was eluted with 100% hexanes, 50/50 hexanes/methylene chloride, 100%
methylene chloride then a gradient of 1% ethyl acetate in methylene chloride to 5% ethyl acetate
in methylene chloride until all material was removed from the column. A total of 7 fractions
were collected. A TLC plate, spotted with all fractions and the crude material, was run in 30%
ethyl acetate/hexanes. The Rf values were calculated for any significant spots. The fractions
containing the pure 4-acetylbiphenyl were combined into a tared round bottom flask and the
solvent was evaporated off by a rotary evaporator. The final mass was obtained and a percent
yield was calculated. Observations were noted as to the appearance (color, odor, size and shape
of crystals) of the product. The melting point of the purified product was determined. A KBr
pellet containing the final product was created and the sample was run to obtain an IR spectrum.

Results
Product Description
The crude product was a white powdered solid with no odor. The purified product was a
mixture of white crystal sheets and granular solids with a slightly sweet odor.

Experimental Data
Mass of Round-Bottom (g) 18.344 g
Mass of Round-Bottom with Product (g) 18.508 g
Pure Product (g) 0.136 g
Melting Point Pure Product 121-122℃
Table 1. Experimental data for purified 4-acetylbiphenyl
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Yield Calculations
Theoretical Yield
1 mol SM 1 mol P 196.2 g P
0.247 g SM ∙ ∙ ∙ = 0.314 g P
154. 2 g SM 1 mol P 1 mol P
Where SM is biphenyl and P is 4-acetylbiphenyl.

Percent Yield
0.136 g
∙ 100 = 43.31%
0.314 g

TLC Data
Rf Value Sample Calculation
distance spot traveled 2.7 cm
Rf = = = 0.63
distance solvent traveled 4.3 cm

Crude TLC (developed in DCM:EtOAc 19:1) Column TLC (developed in 30% EtOAc/Hex)

Crude TLC Column TLC

Spot Rf value Spot Assignment Spot Rf value Spot Assignment
A 0.63 Acetyl chloride standard A 0.35 Crude product
B 0.65 Crude product B 0.79 Biphenyl
C 0.93 Biphenyl standard C 0.55 4-acetylbiphenyl
D 0.34 4,4’-acetylbiphenyl
Table 2. TLC data, including calculated Rf values and spot assignments, for two TLC plates
The presence of the biphenyl indicates that the reaction did not go to completion.

IR Data
The IR spectrum indicated a strong, sharp absorption at 1708 cm-1, which is indicative of the
presence of a carbonyl group in the form of a ketone; this is consistent with the structure of 4-
acetyl biphenyl.
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Conclusion
The synthesis of 4-acetylbiphenyl through a Friedel-Crafts Acetylation of biphenyl and
the subsequent purification of the crude material through flash column chromatography was
successful. The purified product was a mixture of white crystal sheets and granular solids with a
slightly sweet odor. The product was obtained in 43.31% yield.
The isolated purified product was confirmed to be 4-acetylbiphenyl by comparing the
experimental melting point with the known melting point; there was only a 0.5℃ difference
between the two melting points, indicating that the product was a relatively pure sample of 4-
acetylbiphenyl. The product was also be confirmed as 4-acetylbiphenyl by analyzing the spectral
data. The IR spectrum indicated the presence of a ketone due to the peak present at 1708 cm-1,
which is consistent with the structure of 4-acetylbiphenyl. This result is indicative of the fact that
the acetyl group was added, thus proving that the Friedel-Crafts Acetylation occurred.

References
PubChem Open Chemistry Database. Biphenyl.
https://pubchem.ncbi.nlm.nih.gov/compound/Biphenyl (accessed March 2017).

PubChem Open Chemistry Database. Acetyl chloride.

https://pubchem.ncbi.nlm.nih.gov/compound/Acetyl-chloride (accessed March 2017).

PubChem Open Chemistry Database. Aluminum chloride.

https://pubchem.ncbi.nlm.nih.gov/compound/Aluminum-chloride (accessed March 2017).

PubChem Open Chemistry Database. 4-Acetylbiphenyl.

https://pubchem.ncbi.nlm.nih.gov/compound/4-Acetylbiphenyl (accessed March 2017).

Schoffstall, Allen M., Barbara A. Gaddis, and Melvin L. Druelinger. Microscale and Miniscale
Organic Chemistry Laboratory Experiments; 2𝑛𝑑 ed.; New York: McGraw-Hill Higher
Education, 2004. Print; pp 90-91, 270-281.