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Synthesis of Acetyl Ferrocene

Iris Benardete

S4619714

i.benardete@student.rug.nl

Demonstrators: Jacco VanDer Wal & Balint Magyari

21 January 2022

Reaction Scheme

Figure 1. Reaction scheme for the synthesis of acetyl ferrocene

Abstract

In this experiment, acetyl ferrocene was synthesized from ferrocene reacting with phosphoric

acid and acetic anhydride. Column and thin-layer chromatography techniques were used to

separate and purify the components. The products were acetyl ferrocene and diacetyl

ferrocene. They were characterized by melting point and 1H NMR spectroscopy. The

calculated yield for each component was 19% for ferrocene with 0.56 grams of product, 14%

for acetyl ferrocene with 0.506 grams, and 3% for diacetyl ferrocene with 0.16 grams obtained

in total. The melting point of ferrocene was found to be 173.5 ± 0.5°C, and acetyl ferrocene

showed up to have a melting point of 82-85°C. The melting point of diacetyl ferrocene was not

taken due to the small amount of product.

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Inroduction

Ferrocene is an organometallic compound with the formula Fe(C5H5)2. The molecule consists

of two cyclopentadienyl rings bound to a central iron atom. It is an orange solid that is soluble

in most organic solvents. Acetyl and diacetyl ferrocene was synthesized from ferrocene

reacting with acetic anhydride and phosphoric acid in this experiment. The goal was to

accurately purify and separate the components from the mixture using column and thin-layer

chromatography.

Theory

Figure 2. Reaction mechanism for the synthesis of acetyl ferrocene

In the first step of the mechanism, phosphoric acid protonates acetic anhydride to give acetic

acid plus an intermediate called an acylium ion, which is the activated version of the acetyl

group. In the second step, the aromatic π electrons on the ring attack the acylium ion, the

electrophile. Then, the conjugate base removes the proton from the ring, and the product acetyl

ferrocene forms.

Thin-Layer Chromotography

TLC can be used to monitor the progress of a reaction or to purify small amounts of a

compound. In this experiment it was used to separate the compounds accurately and combine
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the test tubes that had the same component to make a proper analysis. TLC is widely used

because of its high sensitivity, speed of separation and simplicity.

Column Chromotography[1]

Column chromatography is an extension of thin-layer chromatography (TLC). Instead of

applying a sample on a thin layer of silica, a sample is put in a cylinder with the according

solvent. Pressure is applied continuously until the components completely drain from the

cylinder. With this technique, components can both be separated into different flasks, and the

mixture can be purified. The same principles of thin-layer chromatography (TLC) apply to

column chromatography. A TLC should always be done before performing a column to

determine the proper solvent ratio.

Experimental [2]

First, ferrocene (3.0 g, 16.1 mmol) was dissolved in acetic anhydride (10 mL) in a 100 mL

round-bottom flask. The flask was cooled in an ice-bath. Phosphoric acid (85%, 2 mL) was

added drop-wise to the mixture while the temperature was being monitored to stay below 25°C.

The ice-bath was replaced with a warm water bath to raise the temperature to 35-40 °C. The

reaction was monitored by TLC (toluene) 10 minutes after the reaction reached 35°C every 30

minutes. The reaction was poured into a 800 mL beaker containing 50 g ice after three hours.

The reaction was stirred in the beaker with NaOH (10%, 75mL) making sure the solution stayed

acidic. Then solid NaHCO3 was added to neutralize the acid. The product was extracted with

ethyl acetate (2x75 mL). It was dried with MgSO4 and concentrated in the rotavapor. The

remaining solid product was weighed and purified with column chromatography. The products

were characterized by melting point and 1H NMR spectroscopy.

1
H NMR and melting point results:

Ferrocene:
1
H NMR spectrum (60 MHz, CDCl3): δ/ ppm = 4.18 ppm (s, 1H).

Melting point was determined to be 173.5 ± 0.5°C.

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Acetyl ferrocene:
1
H NMR spectrum (60 MHz, CDCl3): δ/ ppm = 4.76 ppm (d, J = 1.81 Hz, 2H), 4.51 ppm (d, J=

1.81 Hz, 2H), 4.20 ppm (s, 5H), 2.39 ppm (s, 3H).

Melting point was determined to be in the range of 82-85°C.

Diacetyl ferrocene:
1
H NMR spectrum (60 MHz, CDCl3): δ/ ppm = 4.76 ppm (d, J = 2.29 Hz, 2H), 4.51 ppm (d, J=

1.53 Hz, 3H), 2.40 ppm (s, 3H).

Results and Discussion

After the column and thin-layer chromotography was performed, the three components within

the mixture were succesfully separated. These three components were ferrocene, acetyl

ferrocene and diacetyl ferrocene. A total of 37 test tubes were obtained, 5 of them containing

ferrocene, 4 of them acetyl ferrocene and 3 of them diacetyl ferrocene.

Figure 3. 1H NMR spectrum of ferrocene

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Figure 3 shows the 1H NMR spectrum of ferrocene. The only sharp peak at 4.18 ppm shows

the ten equivalent aromatic protons as a singlet. Due to the symmetry, all ten protons are

chemically equivalent. The peak has an integration of 1.00 due to all protons belonging to a

CH molecule. The melting point of the compound was found to be 173.5 ± 0.5°C. The actual

melting point of ferrocene is 172.5°C which proves that the component was accurately

separated and purified. A total of 0.56 grams of ferrocene was obtained, which gave a yield of

19%. There may have been some mass loss during extraction or column chromatography.

Some of the product may have remained in the other test tubes that the amount was so little

that the TLC results did not show.

Figure 4. 1H NMR spectrum of acetyl ferrocene

The 1H NMR spectrum of acetyl ferrocene is presented in Figure 4. Acylation of one of the

aromatic cyclopentadienyl rings ruins the symmetric structure of ferrocene. The singlet at 2.39

ppm represents the 3 protons belonging to the methyl group, shown as the letter “B”. It has no

neighboring protons and gives an integral of 3 due to the CH3 group. The singlet at 4.20 ppm,
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assigned as “D”, represents the 5 protons belonging to the unsubstituted cyclopentadienyl ring.

All protons are chemically equivalent due to the symmetry of the ring. The integration of 5 is

due to the 5 symmetric aromatic protons. The doublets on 4.76 and 4.51 ppm represent the

protons on the substituted cyclopentadienyl ring. The two ring protons close to the acetyl group

are more deshielded and therefore shift more towards the downfield. The other ring protons

that are not neighboring the acetyl group are more shielded and result in a lower chemical

shift. The melting point of the compound was found to be between 82-85°C. This melting point

also shows that the product was correctly separated and purified due to the real melting point

of acetyl ferrocene being between 81-85°C. A total of 0.504 grams were obtained giving a yield

of 14%.

Figure 5. 1H NMR spectrum of diacetyl ferrocene

Figure 5 shows the 1H NMR spectrum for diacetyl ferrocene. A very similar spectrum to acetyl

ferrocenes was expected but wasn’t obtained. The only difference was supposed to be the
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lack of the signal belonging to the protons in the unsubstituted ring of acetyl ferrocene.

Similarly, in this spectrum, the singlet at 2.40 ppm represents the proton signals coming from

the methyl groups belonging to the acetyl group with an integration of 3. The multiplets at 4.76

and 4.51 ppm, assigned as “A” and “B”, are signals coming from the ring protons. The protons

that are close to the acetyl group are more on the downfield due to being more deshielded.

The rest of the peaks may be caused by various impurities that have not been properly purified.

The TLC’s done for this component, diacetyl ferrocene, had very blurry dots appearing, which

may have been a sign that very little product had been obtained and separation was not done

accurately. A total of 0.16 grams of this component was obtained, giving a yield of 3%. The

extremely low yield of the product also indicates that the separation and purification were not

successful. Due to the very small amount of product, a melting point analysis has not been

able to be made.

Conclusion

In conclusion, the components were successfully separated from each other using column and

thin-layer chromatography. Acetyl ferrocene was synthesized and purified. The component

diacetyl ferrocene was not accurately purified according to its 1H NMR spectrum. The melting

points of ferrocene and acetyl ferrocene were determined to be 173.5 ± 0.5°C, and 82-85° C

in the respective order. The yield of the three components was calculated as 19% for ferrocene,

14% for acetyl ferrocene and 3% for diacetyl ferrocene.

References

[1] Libretexts. “2.4: Column Chromatography.” Chemistry LibreTexts, Libretexts, 5 Mar.

2021,

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Organic_Chemistry_Lab_Techni
ques_(Nichols)/02%3A_Chromatography/2.04%3A_Column_Chromatography.

[2] Student manual practicum for Synthesis and Analysis 1. January 2022.