Name: Vaibhav PAL

Registration number:MS15051
AIM: To observe Acetylation of ferrocene.
Materials Required: beaker, RB flask, glassrod, buchner, funnel,
filterpaper,hot water bath, ice bath, litmuspaper, clamp.
Theory: Acylation of aromatic ring is accomplished by Friedel-Crafts
reaction using an acid as a catalyzator. In ferrocene (bis(η 5-
cyclopentadienyl)iron), two cyklopentadienyl aromatic rings
coordinating to a central atom Fe(II) are found. Using mild condition
(phosphoric acid and acetic anhydride) yields a monoacetylated product
besides unchanged ferrocene (Scheme 1). The mixture is then
separated by elution chromatography.

O O +
H3C C O
+  H 3PO4 + H 2PO4­  + CH 3COOH
O
H3C C O
+

+ CH3
H3C C O
Fe + Fe O +  H +
H3C C O
+

1 Acetylation of ferrocene by phosphoric acid/acetic anhydride mixture

The most common combination of reagents used for Friedel-Crafts

acetylation is a mixture of anhydrous aluminium(III) chloride and acetyl
chloride. The reaction requires anhydrous condition and is done in DCM
(dichlormethane). The reaction mixture is protected by CaCl 2 drying
tube or it is carried out in inert atmosphere of nitrogen gas. The
reaction has a tendency to over-react forming di-substituted product.
This can be controlled by changing a molar ratio of the reactants. An
inactivation effect on the aromatic ring of the acetyl group leads
preferably to a formation of 1,1’-diacetylated product. 1,2-diacetylated
ferrocene and 1,3-diacetylated ferrocene are the minor products.

This Friedel-Crafts acylation of ferrocene produces acetylferroceneby

using acetic anhydride in the presence of a catalytic amount of
phosphoric acid. A frequently used catalyst for such acylations is
aluminumtrichloride, but in this particular acylation that catalyst
complicates the process by producing a disubstituted product: l,l'-
diacetylferrocene. Themilder catalyst, phosphoric acid, works better. It
generates the acyliumion electrophile by protonation followed by loss of
acetic acid. No organic solvents are used, although one of the reactants,
acetic anhydride, is used in excess and thus may play the role of a
solvent in this reaction. Unfortunately, these acylation conditions are
not general - it is the relatively high reactivity of ferrocene, compared to
simpler aromatic substrates, which allows the replacement of AlCl3 with
phosphoric acid. Discovery of new Friedel-Crafts-like reaction chemistry,
applicable to simple benzene derivatives, remains an area of ongoing
investigation

Procedure:
1. Place 2g of sublimed Ferrocene in a 25 mL round-bottom flask with a
magnetic stir bar. Add 6.35 mL of Acetic Anhydride using a dry Pastuer
pipet. Add 1.3ml 85% Orthophosphoric Acid using a 1 mL syringe. Cap
the flask with a septum and push a clean needle through the septum.
This will minimize the amount of moist Air that enters the flask, and
allow for release of any gas evolved.
2. Dissolve the Ferrocene by gently heating the flask on a heating the
flask on a sand bath while carefully stirring and agitating the flask.
3. Continue heating for an additional 10 minutes and then place the
flask in an ice-bath.
Remove the needle and septum, and carefully add 0.5 mL of ice-cold
Water drop wise with a thorough mixing.
4. Neutralize the resulting solution against litmus by drop wise addition
of a 3M aqueous solution of Sodium bicarbonate. Avoid an excess of
base.
5. Filter the mixture by vacuum filtration, rising out the flask and
washing the solid collected with cold water. Remove the solid from the
filter and place it on a filter paper. Press the product as dry as possible
between sheets of filter paper. Recrystallize using hexane solvent.
6. Separate the crude product via column chromatography. Use Alumina
as the packing material and form your initial slurry using Pet Ether.
Apply your solid to the column by dissolving it in a minimum amount of
Dichloromethane, adding 300 mg Alumina, heating to remove the
Dicholoromethane and then applying the mixture to the column. Wash
the compound onto the column using a small amount of Pet Ether. Elute
the compound with several small portions of Pet Ether. Elute any
Ferrocene with Pet Ether. Then, elute the Acetyl Ferrocene with a 50:50
mixture of Pet Ether and t-Butanol.
7. Collect the Acetyl Ferrocene, evaporate the solvent and weigh the
product. Determine your percentage yield.

Observations:

(C6H5)2Fe + (CH3COO)2 + H3PO4 → C12H12FeO + CH3COOH

Molar mass of (C6H5)2Fe= 186.04 g/mol

Weight of ferrocene taken= 2g
Moles of ferrocene used in the experiment= 2/186.04=0.01075 mol
=10.75mmol
Molar mass of acetic anhydride= 102.09 g/mol
Volume of acetic anhydride= 6.6 ml
Density=1.08 g/cm3
Weight = 1.08* 6.6= 7.128 gt
Moles= 7.128/ 102. 09= 0.069
So ferrocene is the limiting reagent.
1 mole of ferrocene will produce 1 mole of acetoferrocene.
So 0.01075 moles of ferrocene will produce 0.01075 moles of
acetoferrocene.
Molar mass of acetoferrocene= 228.07 g/mol
Theoritical Yield= 0.01075*228.07=2.45g
Experimental yield of the crystallized product= 0.505 g
Percentage yield = 0.505/2.45*100= 20.6 %

Result:
Red coloured crystals of acetoferrocene with some unreacted ferrocene
was observed.

Precautions:
 Eye protection should be worn at all times while using this
instrument.
 Phosphoric acid is a strong dehydrating agent.
 Wear protective gloves when pouring concentrated phosphoric
acid. Acetic anhydride can burn the skin. Pour acetic anhydride in
a fume hood. Avoid contact with skin and clothes.
References:
1.http://chem.pieceofscience.com/?p=1349
2.Inorganic Chemistry: Principles of Structure and Reactivity - James E.
Huheey.
3.https://ch337tyronespowerhour.wikispaces.com/Acylation+of+Ferroce
ne
4.Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the
Elements (2nd ed.).