An Enhanced Chromatographic Technique

for the Preparative Scale Purification of Acetyl Ferrocene

James Davis and D. Huw Vaughan
Department of Chemistry and Chemical Engineering, Sensors Group,
University of Paisley, High Street, Paisley, Scotland PA1 ZBE, UK
Marco F. Cardosi
Department of Biology, Sensors Group, University of Paisley, High Street, Paisley, Scotland PA1 2BE, UK
Acetyl ferrocene serves not only as the starting material The preparation of
for a large number of ferrocene derivatives, but also it has the acetyl derivative
a varied range of properties that make it suitable for incor- is well documented
poration into undergraduate laboratory courses (1).Its use (2-7) b u t we have
in such courses, however, has been limited by the time-con- found that by modify-
suming problem of purifying significant quantities of the i n g several pre-
material. The small-scale preparation of acetyl ferrocene viously published
and its subsequent analysis by several chromatographic methods we can
techniques, including liquid column ( 2 , 3 ) ,thin layer (41, minimize the forma-
high performance liquid (5, 6)and dry column chromatog- t i o n of intractable
raphy (7),have been well documented. These reports have t a r s caused by de-
been invaluable in demonstrating the ability of chromatog- composition prod-
raphy to study the course of the acetylation reaction and to u c t s , t h e r e b y pro-
the identification of the reaction products. However, al- longing the life of the
most all of the previously mentioned techniques are un- column. If another
suitable for the large preparative scale purification of this route is used in the
versatile compound. High performance liquid chromatog- preparation of t h e
raphy would have been the method of choice but the mi-
croliter scale volumes are a major restriction and although /\ \7 1 crude material. care
To water should be t a k k n to
J b p Pump avoid the ~roduction
simple liquid column procedures are more common to
preparati;e scale separations they are unfortunately ex- of the decomposition
tremely slow, with several hours needed to elute even mod- products, the diacetyl
est amounts of the compound. To overcome this problem a n d o t h e r bypro-
we have developed a variation of flash column chromatog- ducts,
Chromatography apparatus.
raphy that can reduce dramatically the elution time of the
various fractions. from the normal period of several hours
to a matter of minutes, and which ltilizes standard labo- Preparation of Acetyl Ferrocene
ratorv glassware. Caution: Protective gloves should be worn when handling
In this modified chromatographic technique, suction (by these reagents.
. . is applied
means of a water pump) .. to the bottom of the
Ninety percent phosphoric acid (1.5 mL) is slowly added
column allowing the two fractions, corresponding to the
the product acetyl ferrocene and unreacted ferrocene, to be to a stirred solution of ferrocene (1.5 a) and acetic anhv-
eluted cleanly and rapidly. The apparatus used in the pu- dride 15 mL conteined in a 100-mL round hortomsd f l a s ~ .
rification mocess is detailed in the firmre and consists of a Thc flask la rhcn fitted with a calc~umchloride w a r d tub(!
100-mL separating funnel with a glass wool plug. The fun- and placed in a water bath maintained a t 50 "C. After a
nel is filled with a s l u m of silica eel' orepared using the period of 10 min, the mixture is removed and poured into
etherlethyl acetate mixture descriied be&, leavingjust a 0.25 M sodium acetate solution. The resulting mixture is
cooled in ice and 50 mL of dichloromethane added.
enough suace a t the to^
u . . to .lace the crude acetvl ferrocene.
The column is connected to a water pump via a trap with C a u t i o n : Cnrc ihoulo hc rnkcn when handling the .ulvt.nts.
250-mL conical flasks serving a s the collecting vessels. The c,prcinllg d~chloromclhnnc,2nd thcir u?e. where pc+ciblt.
solvent mixture used to elute the unreaded ferrocene was should he rc;triclcd t o n n cfficcnl fume hood.
96% ~etroleumether (40-60 " C )and 4% ethvl acetate (bv . .
volume). The acetyl derivative can be eluted speedily using The orange organic layer is separated and retained and
pure ethyl acetate. the dark, brown-colored aqueous layer washed with a fur-
- ther 20 mL of dichloromethane. The organic fractions are
'The ab ily lo regenerate tne colmn means tnal it neea on y oe combined and aash(vl with wlter liillowrd bv saturated so-
prepared once dur ng a normal acaaem c lerm Tn s fcat~re al ows I dium bici~rl~matc 'lht:orannic li~verir dried with
;i~~luti(~n.
to be constructed bva technician, thus removing the risk of students anhydrous magnesium sulfate a n l t h e c&le acetyl deriva-
being exposed to the silica gel powder and the problems associated tive obtained bv removal of the solvent on a rotarv evavo-
with its handling and disposal.
Caution: In the event of students being permitted to pre-
pare the packing material, they should be made aware ofthe
-
hazards involved in handline the fine oowder and
should take the proper precautions.
Aslurry of the crude acetyl ferrocene (approx. 1g) is pre-
pared using the petroleum etherlethyl acetate solvent mix-

266 Journal of Chemical Education

ture and placed on top of the column. Aquick-fit cylinder is
then added and filled with solvent. The separating funnel
valve i s opened and the water pump activated. Then the
yellow of the unreacted ferrocene will move rapidly down
the column. The rate of elution can be controlled by ma-
nipulating either the air valve connected to the trap or the
water tap directly, although the latter method is not rec-
ommended i n ease of water suck back. Once the yellow of
the ferrocene is no longer present on either the column or
in the eluant stream the collectinp - vessel should be re-
placed, in preparation for collecting the acetyl derivative.
The solvent svstem also is changed to uure ethyl acetate
instead of the petroleum ether kixture. suction is reap-
plied and the red band due to the acetyl derivative re-
moved from the column. When both fractions have been
collected, the silica gel may be regenerated by passing 100
mL of the petroleum etherietbyl acetate mixture through
the column. The acetyl derivative is obtained by removing
the solvent on a rotary evaporator with the purity being
quickly determined by thin-layer chromatography on silica
strips using a petroleum ether (90%)/ethyl acetate
(10%) solvent mixture, with one spot due to the product
being observed.
Conclusion
The majority of undergraduate laboratoq. experiments
involving acetyl ferrocene have focused on the small-scale
preparation and chromatographic identification of the re-
action products. The experiments described by Vogel (11,
however, have shown that this compound is far more ver-
..
satile and aoolicable to a wide range of chemical tooics
from simple acid-base behavior to cyclic voltammetry The
main contributing factor i n its limited use has been the
problem of o b t a ~ k n gsufficient quantities of the com-
pound. By using the technique described above i t is now
possible to obtain significant amounts of the material, with
the complete preparation including purification taking
only about one hour. This time scale coupled to the fact
that the apparatus may be reused allows the incorporation
of a greater variety of ferrocene chemistry into under-
graduate laboratory courses.
Literature Cited
1. V@. 0. C.; Peny W. D , J , Chem. Edue 1991.68.607-608.
2. Bozak, R.E. J. Chem. Edur. 1966,43,73.
3. Wade, L . 0 . J Chem Edur 1976,SS.208.
4 . Hew, J. E J Chem. Educ 1966.43.599.
5 . Hsworth, D.T: Liu.T.J.J.Chem. Edue. 1976.53.730.
6. McKone. H.T J. Chem. Edue 1960,S7,380-381.
7. Gi1beit.J.C.;Monti. S. A. J. Chsm. Educ 1973.50.369-370.
'~olygramSilica G/UV, (0.25-mm layer)
Volume 72 Number 3 March 1995 267