Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 8, pp. 1435−1439.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
G.G. Abashev, A.D. Antuf’eva, A.Yu. Bushueva, P.G. Kudryavtsevd, I.V. Osorgina, R.V. Syutkin, E.V. Shklyaeva, 2010, published
in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 8, pp. 1330−1334.
Ferrocenes Conjugated with Thiophene, Carbazole,
and Pyrimidine Fragments: Synthesis and Properties
G. G. Abashev
, A. D. Antuf’eva
, A. Yu. Bushueva
, P. G. Kudryavtsev
I. V. Osorgina
, R. V. Syutkin
, and E. V. Shklyaeva
Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia
Natural Science Institute, Perm State University, Perm, Russia
Perm State University, Perm, Russia
Trivektr Research and Production Enterprise, Limited Liability Company, Perm, Russia
Received March 10, 2010
Abstract—Ferrocenyl-containing chalcones containing π-excessive heterocyclic fragments capable of
electrochemical polymerization (carbazole, thiophene, 2,4-ethylenedioxythiophene) were prepared by the Claisen–
Schmidt reaction. 2,4,6-Trisubstituted pyrimidines derived from them were synthesized.
The properties of ferrocene and its derivatives
attract steady interest of researchers in many ﬁ elds of
organic and organometallic chemistry. Wide range of
studies of applied properties of ferrocene is due to its
speciﬁ c physical and chemical properties: unusually
high (for organometallic compounds) thermal stability,
high vapor pressure, low toxicity, good solubility in
organic solvents, and diverse chemical transformations.
The use of electrochemical properties of ferrocene is
based on readiness and reversibility of one-electron
redox processes. The ferrocene–ferricenium cation
system is one of the most highly reversible redox
systems. Thanks to this property, this redox couple
has found wide practical use: as reversible electrodes
in analytical chemistry and as electron-transfer agent
in various systems (primarily in biochemical studies)
[1, 2]. Recently there has been growing interest in the
use of ferrocene-containing organic compounds in such
ﬁ elds as nonlinear optics  and chemosensorics . It
was also shown that compounds containing a ferrocene
fragment can penetrate through cell membranes .
At the same time, it is known that such heterocycles
as pyrrole, thiophene, and pyrimidine are widely used
in fabrication of conducting and electroluminescent
materials . A combination of the properties of
ferrocene and such heterocycles could lead to new
unique properties of materials, i.e., nonlinear optical,
magnetic, or electrochemical properties.
From acetylferrocene I and diacetylferrocene VIII
prepared in advance, we synthesized ferrocene-containing
chalcones containing unsubstituted thiophene (V, IX)
and carbazole (VI) fragments, described previously
, and 3,4-ethylenedioxythiophene fragment (VII)
(Scheme 1). The Claisen–Schmidt condensation used
in our study can be performed by diverse procedures.
We used either reﬂ uxing of a mixture of aldehyde and
ketone in 2% aqueous alkali solution (chalcones V, VII,
IX) or heating in a 10% solution of KOH in methanol
(chalcone VI). Relatively recently a procedure was
described for preparing chalcone VI without solvent
. All the compounds obtained have bright color: red
(V–VII, X) or violet (IX).
The chalcones prepared were subsequently used
for synthesizing ferrocene-substituted pyrimidines
by cyclization with guanidine sulfate in aqueous
solution  or with guanidine nitrate in dioxane 
in the presence of alkali. Under these conditions,