Stanly Soto

Partner: Cristal Hernandez

TA: Sami Abdulkadir
Class: CHM 2211L Section 016
10/8/2018

Friedel-Crafts Acylation of Ferrocene

Introduction/Background:
A Friedel-Crafts alkylation is a type of reaction that allows for the synthesis of alkylated

products thru the reaction of arenes with alkenes or alkyl halides (Friedel-Crafts Acylation). One

example of a Friedel-Crafts alkylation reaction is Benzene getting alkylated with ethyl bromide

in the presence of FeBr3 which would produce 1-ethyl benzene, FeBr3 and HBr. In this reaction

the Bromine in ethyl bromide would start to bond to the FeBr3 then the electrons in one of the

double bonds in the benzene would be used to bond to the carbon in the ethyl bromide that is

attached to the bromine. One of the bromines in FeBr4- then deprotonates the benzene at the

location where the ethyl group attached itself and the bromine that deprotonates breaks away

from the FeBr3 which leaves the product listed above. A Friedel-Crafts acylation is a reaction

between arenes and acyl chlorides or anhydride to synthesizes an acylated product (Friedel-

Crafts Alkylation). A Friedel-Crafts acylation of benzene requires aluminum chloride as a

catalyst (Weldegirma). However, ferrocene does not require alumina (aluminum chloride) as a

catalyst because it has a high pie electron density which allows it to be acylated under milder

conditions (Weldegirma). One example of a Friedel-Crafts acylation is reacting ferrocene with

anhydride and phosphoric acid to produce acetyl ferrocene and acetic acid. In this the acid reacts

with the anhydride first to form the acylium cation, which will serve as the electrophile

(Weldegirma). When the acylium cation is formed it then reacts with the ferrocene to form acetyl

ferrocene. In this reaction one has to be careful not to add too much acid or anhydride because

they may over acylate and produce diacetylated ferrocene instead of the desired product.
 Mechanism of the synthesis of Acetylferrocene

Possible side reaction in the synthesis of Acetylferrocene

This can result from adding too much anhydride or too much H2PO4.
Procedures:
1. To a small test tube add 40 mg of ferrocene, followed by 0.35 ml of acetic anhydride and

1 ml of 85% phosphoric acid.

2. Then warm the test tube in steam bath, make sure to agitate the content in the test tube to

make sure it dissolves.

3. Heat in the steam bath for 10 minutes.

4. Spot solution on a TLC plate.

5. Once the reaction is complete cool test tube in ice bath.

6. Add 2 drops of ice water to the test tube while mixing.

7. Add 3M NaOH until the pH is neutral (use litmus paper to determine)

8. Once the pH is neutral collect the product using a Hirsch funnel thru vacuum filtration.

9. Wash the test tube thoroughly with water.

10. Dry the product (air dry).

11. Weight the product (Crude) and save a bit for melting point & TLC

12. Prepare a micro-column with wool at the bottom, 1 gram of Alumina, and a bit of sand on

top of the alumina.

13. Wet the column content with hexanes.

14. Transfer the crude product using hexane.

15. Add hexane and begin eluting product from the column into a 50 ml beaker.

16. Label the beaker fraction 1, it should have orange- yellow content.

17. Prepare a 50:50 hexanes to ether solution and add it to the column.

18. Elute the product into a second beaker and label it fraction 2, it should be an orange-red

content.

19. Take a TLC

20. Evaporate solvent from each fraction, collect what is left.

21. Find weight, melting point, % yield, 1H NMR, & % recovery from crude product.
Table of Chemicals:
Chemicals Physical state Hazards Molecule
Solid with a molecular
very hazardous if
weight of 186.04
ingested, skin &
Ferrocene g/mole. Boils at
eye irritant, &
(C 10 H10 Fe) 249°C and melts at
hazardous if
173.5°C & is soluble
inhaled.
in cold water.

Clear colorless liquid Hazardous if

with slight gasoline ingested, inhaled
Hexane smell. Boils at 68℃, & as a skin
(C6 H14) melts at -95℃, & has permeator. Also
a molecular weight of skin & eye
86.18 g/mole contact irritant.

It is a colorless liquid It is an eye irritant,

with a sweet odor. skin irritant &
Toluene Has a molecular permeator, &
(C7 H8 ) weight of 92.14 g/mole hazardous if
boils at 110.6°C & inhaled or
melts at -95°C. ingested.

Clear colorless & Very hazardous as

Phosphoric acid odorless viscous skin & eye irritant.
liquid. Has a melting It is also a skin &
(H3 PO4 )
point of 21℃ & eye corrosive &
boiling at 158℃. lung sensitizer.
Light liquid with a
extremly
strong smell. Has a
hazardous if
Acetic anhydride molecular weight of inhaled or ingested
102.09g/mole has a
(CH3 CO)2 also as a skin &
melting point of -
eye irritant. Also, a
73.1℃ & boils at skin permeator.
139.9℃.
It is a white odorless
Hazardous if
solid. Has a molecular
inhaled or
Alumina weight of 101.96
ingested. Can
(Al2 O3 ) g/mole, mlting point is
cause skin & eye
2072°C & boiling is at
irritation.
2980°C.
Irritant, corrosive,
Odorless solid with a & permeator in
Sodium
molecular weight of case of skin
Hydroxide
40g/mole. It is easily contact. Corrosive
(NaOH)
soluble in cold water. in case of eye
contact.
clear liquid with
alcohol like odor. very hazardous if
Ethanol
MW=46.07 g/mole, ingested, eye &
(CH3 CH2 OH)
boils at 78.5°C & skin irritant.
melts at -114.1°C
Result:
The finished product looked like an orange liquid that when allowed to dry became an

orange solid powder.

Chemical Weight Melting point Rf

Ferrocene 40 mg 173℃ 0.872
Crude
39 mg 130℃ 0.255
Acetylferrocene
Acetylferrocene 39 mg 128℃ 0.17

Percent yield = (Actual yield/Theoretical yield) * 100

= (0.039g / 0.040g) * 100

= 0.975 * 100

Percent Yield = 97.5% of Crude Acetylferrocene

Percent recovery from crude = (Actual yield/Theoretical yield) * 100

= (0.039g / 0.039g) * 100

Percent recovery from crude = 100%

Rf value = spot distance / solvent front

Rf ferrocene = 4.1 / 4.7 = 0.872

Rf Crude Acetylferrocene= 1.2 / 4.7 = 0.255

Rf Acetylferrocene= 0.8 / 4.7 = 0.17

Discussion:
The melting point observed for our starting material was 173℃ which is the literature

value. The melting point of our crude acetylferrocene was observed at around 130℃ which

makes sense because it went down from the starting material melting point, ferrocene 173℃,

which means it was no longer ferrocene. The product in this experiment has a lower melting

point than ferrocene so the fact that the crude melting point went down is good. The melting

point for acetylferrocene observed was 128℃ which is very far off the literature value of about

85℃. A possible side product in this experiment was diacetyl ferrocene which has a melting

point of about 128℃ which is what our observed value for the melting point of ferrocene was.

It’s possible that since we measured out less ferrocene than needed and added the correct amount

of anhydride and acid that we over acetylated the ferrocene and made diacetyl ferrocene instead

of the intended product. The percent yield for our crude product was 97.5% and that is a great

yield. The percent recovery from the crude to the final product was 100% but since 100%

efficiency is not yet possible because some materials are lost to the environment this 100% yield

could be due to the limitations of the scale used. The scale only goes to three decimal places and

values very rarely stay constant, that is too say it moves from40.256 to 40.258 to 40.253 for

example. The TLC helps to determine if the reaction is accruing as it is supposed to by showing

how each, ferrocene, crude, & acetyl ferrocene, move thru the plate. In the TLC plate ferrocene,

the starting material, is supposed to climb higher on the plate and the product, acetyl ferrocene,

lower down on the plate. The crude should be somewhere in between. So, by comparing the

starting to crude to product on the TLC one could make a good inference if the desired product

was achieved based on if the product is lower on the TLC as compared to the starting material or

if is the same level then the ferrocene was not converted. Problem 1 There are four observable

peaks and the first is at about 2.4 ppm and I think that this singlet belongs to the CH3 group in
the acetyl group attached to the ferrocene in the image the CH3 group is labeled as d. The reason

I chose the CH3 group for this first peak is because on top of the peak it says 3 which is

corresponding to how many protons are giving that same signal and the three protons in CH3 fit

that bill. The next peak is at about 4.3 ppm and has five protons giving the same signal and that

would match c in the image which is the five protons of the unsubstituted cyclopentadienyl ring.

The next peak is at about 4.6 ppm which has a two on it and this would belong to the two protons

labeled b. This is because they are more shielded than the two other protons which means a

lower ppm. The last peak also has a two on it and is at about 4.7 ppm which means the protons

are more deshielded than the last peak, so they are the ones labeled a. The acetyl group is

deshielding, so it moves the values further down field for the closer protons. Problem 2, based on

the melting point and the 1H NMR I would say that their product is crude. The melting point

observed of 75-78℃ is below the literature value of 85-86℃. The 1H NMR presented also has

inconsistencies that do not allow it to match that of acetyl ferrocene. While their first, third, and

fourth peaks matched those of acetyl ferrocene their second peak has 15 proton readings instead

of 5. Based on the NMR it looks like acylation occurred but something else happened that altered

the product.

Conclusion:
The main objective of the lab was to synthesize acetyl ferrocene by reacting ferrocene

with acetic anhydride thru Friedel-Crafts acylation reaction. Based on the data collected like the

melting points we concluded that the product made in this experiment was not acetyl ferrocene

but diacetyl ferrocene which was a possible side product. We probably used too much anhydride

which led to over acylation which resulted in diacetyl ferrocene being the product in our

experiment. Friedel-Crafts acylation reactions are very important in our bodies, DNA is one
example of things in our body that has an aromatic compound but since aromatics are so stable it

is difficult for it to react with anything else so one way our body works around it is thru Friedel-

Crafts acylation. The objective of the lab was not met because the data reveled that our product

was not acetyl ferrocene.

Reference:
Weldegirma, S. Experimental Organic Chemistry: Laboratory Manual for CHM 2210L

and CHM 2211L, Tampa: FL; pp 103-107

Material Safety Data Sheet (MSDS) List. ScienceLab: Chemicals & Laboratory

Equipment.

Friedel-Crafts Acylation. https://www.organic-chemistry.org/namedreactions/friedel-

crafts-acylation.shtm (accessed Oct 7, 2018).

Friedel-Crafts Alkylation. https://www.organic-chemistry.org/namedreactions/friedel-

crafts-alkylation.shtm (accessed Oct 7, 2018).