Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 2, pp. 340−342.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
R.I. Khusnutdinov, A.R. Baiguzina, R.R. Mukminov, U.M. Dzhemilev, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol.
82, No. 2, pp. 346−348.
New Procedure for Synthesis Alkyl Esters
of 5-Acetyl-2-Furan-Carboxylic Acid Alkyl Ester
R. I. Khusnutdinov, A. R. Baiguzina, R. R. Mukminov, and U. M. Dzhemilev
St. Petersburg State Polytechnical University, St. Petersburg, Russia
Received January 13, 2009
Abstract—The possibility to synthesize alkyl esters of 5-acetyl-2-furan-carboxylic acid by the reaction of 5-
acetyl-2-furan with CCl
and aliphatic alcohols under the action of iron-containing catalysts was studied.
Furan derivatives ﬁ nd wide application as starting
compounds in the synthesis of pharmaceuticals. Thus,
2-furan-carboxylic acid and its esters possess anti-
tumor activity , and methyl ester of 5-acetyl-2-furan-
carboxylate (I) is used as a starting compound in the
synthesis of pharmaceuticals applied to treatment and
prophylaxis of mammals’ peptide cankers .
The majority of known procedures for the preparation
of methyl 5-acetyl-2-furan-carboxylate (I) are based on
a catalytic acylation of 2-furan-carboxylic acid esters by
acetic anhydride. When H
is used as the acylation
catalyst the yield of I is only 0.5% , whereas in the
presence of fourfould SnCl
excess it reaches 96% .
With the aim to develop a new procedure for the
synthesis of methyl 5-acetyl-2-furan-carboxylate (I),
we studied the possibility of introducing the CO
group in a molecule of 2-acetylfuran (more accessible
than the methyl 2-furancarboxylates ) by means of
a new procedure successfully tested on thiophene and its
derivatives . The essence of the procedure consists in the
interaction of thiophenes with the system CCl
catalyst: under the action of the catalyst thiophene is
alkylated by CCl
to form 2-trichloromethylthiophene,
which then undergoes alcoholysis to form methyl 2-
thiophenecarboxylateic acid. Starting the study of the
reaction of 2-acetyl-2-furan with the system CCl
OH−catalyst, it was necessary to take into account
the pronounced tendency of the furan cycle to opening, as
the attempt to realize the above-mentioned reaction using
furfulyl alcohol as an example was unsuccessful and has
led to obtaining methyl ester of levulinic acid .
It has been shown that methyl 5-acetyl-2-furan-
carboxylate (I) is the main product of the reaction between
2-acetylfuran and the system CCl
the catalysts we have tested compounds and complexes of
Ni, Cu, Mn, Pd, V, and Fe, which have the common ability
to labilize the C-Cl bond in the CCl
molecule [7, 8].
Among the compounds and complexes, which have
shown catalytic activity, iron derivatives form the
following series: Fe(acac)
(95%) > Fe(C
(87%). The reaction proceeds at 120ºC and is
completed within 9 h by the full conversion of initial
CO + CCl
120 C, 9 h
The structure of compound I was confirmed by
the methods of one-dimensional [
С, and APT
(Attached proton treatment) NMR spectroscopy] and
two-dimensional NMR spectroscopy [HMBC (Hetero
Multiple-bond Correlation)]. The 2,5-position of the