ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 6, pp. 930−934. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © N.G. Gileva, S.I. Kuznetsov, S.N. Salazkin, V.A. Kraikin, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 6, pp. 859−863.
ORGANIC SYNTHESIS AND INDUSTRIAL
4',4''-Bis(2-carboxybenzoyl)diphenyl Sulfone Pseudodichloride
as a New Monomer for Polyarylenephthalides
N. G. Gileva
, S. I. Kuznetsov
, S. N. Salazkin
, and V. A. Kraikin
Ufa Institute of Chemistry, Russian Academy of Sciences, pr. Oktyabrya 71, Ufa, Bashkortostan, 450054 Russia
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia
Received June 30, 2015
Abstract—A procedure was developed for oxidation of 4',4''-bis(2-carboxybenzoyl)diphenyl sulﬁ de with per
acids (peracetic and triﬂ uoroperacetic). The 4',4''-bis(2-carboxybenzoyl)diphenyl sulfone obtained was converted
into pseudodichloride, and three new polyarylenephthalides with regular alternation of the electron-acceptor
(diphenyl sulfone) and electron-donor (diphenyl oxide, diphenyl sulﬁ de, terphenyl) fragments were synthesized
on its basis. The synthesized monomers can be used in the synthesis of new polyarylenephthalides exhibiting the
electronic switching effect.
Polyarylenephthalides, along with high resistance
to heat and chemicals and with good solubility and
ﬁ lm-forming properties, exhibit speciﬁ c electrophysical
properties [1–4]. Much attention has been given recently
to properties of thin ﬁ lms of polyarylenephthalides, in
particular, to their transition into a highly conducting state
(electronic switching effect) under the action of various
external factors: pressure, electric and magnetic ﬁ elds
[4–6]. These facts stimulate further studies concerning
synthesis and properties of new polymers of this class.
One of the research directions is synthesis of new
polyheteroarylenephthalides with electron-donor and
electron-acceptor fragments alternating in the backbone.
In conjugated polymers, such alternation allows
preparation of structures with a narrow conduction band
[4–6], which ﬁ nd use in such ﬁ eld of organic electronics
as photovoltonics [4–7].
In the ﬁ rst step of the synthesis performed in this
study, 4',4''-bis(2-carboxybenzoyl)diphenyl sulfide
was converted to 4',4''-bis(2-carboxybenzoyl)diphenyl
sulfone by oxidation of sulfide groups to sulfone
groups . The resulting product was then converted to
pseudodichloride containing a strong electron-acceptor
group (a new monomer for polyarylenephthalides), which
was then involved in polycondensation with electron-
donor monomers: diphenyl oxide, diphenyl sulfone, and
The starting compounds and solvents were puriﬁ ed
by standard procedures [9–11].
4',4''-Bis(2-carboxybenzoyl)diphenyl sulﬁ de (1) was
synthesized according to .
4',4''-Bis(2-carboxybenzoyl)diphenyl sulfone (2).
A 50-mL ﬂ ask was charged with 1 g of ﬁ nely ground
4',4''-bis(2-carboxybenzoyl)diphenyl sulﬁ de (1), 20 mL
of 36% hydrogen peroxide, and 10 mL of glacial acetic
acid (or triﬂ uoroacetic acid, or acetic anhydride). The
heterogeneous reaction mixture was stirred on a magnetic
stirrer for 24 h at room temperature with intermittent
sampling to determine the degree of conversion. The
intermediate samples and the ﬁ nal product after the
reaction completion were transferred into distilled water.
The white precipitate was ﬁ ltered off, washed with three
portions of distilled water, and dried in air at 120°С to
The ﬁ nal product, 4',4''-bis(2-carboxybenzoyl)di-
phenyl sulfone (2), was recrystallized two times from
a methanol–water mixture (2 : 1), ﬁ rst in the presence