4′,4″-bis(2-carboxybenzoyl)diphenyl sulfone pseudodichloride as a new monomer for polyarylenephthalides

Article abstract of DOI:10.1134/S1070427215060063

A procedure was developed for oxidation of 4′,4″-bis(2-carboxybenzoyl)diphenyl sulfide with per acids (peracetic and trifluoroperacetic). The 4′,4″-bis(2-carboxybenzoyl)diphenyl sulfone obtained was converted into pseudodichloride, and three new polyaryle

Full text of DOI:10.1134/S1070427215060063

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
ORGANIC CHEMISTRY
4',4''-Bis(2-carboxybenzoyl)diphenyl Sulfone Pseudodichloride
as a New Monomer for Polyarylenephthalides
N. G. Gilevaa, S. I. Kuznetsova, S. N. Salazkinb, and V. A. Kraikina
a Ufa Institute of Chemistry, Russian Academy of Sciences, pr. Oktyabrya 71, Ufa, Bashkortostan, 450054 Russia
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia
e-mail: gilevang@anrb.ru
Received June 30, 2015
Abstract—A procedure was developed for oxidation of 4',4''-bis(2-carboxybenzoyl)diphenyl sulfide with per
acids (peracetic and trifluoroperacetic). 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 sulfide, terphenyl) fragments were synthesized
on its basis. The synthesized monomers can be used in the synthesis of new polyarylenephthalides exhibiting the
electronic switching effect.
DOI: 10.1134/S1070427215060063
Polyarylenephthalides, along with high resistance
to heat and chemicals and with good solubility and
film-forming properties, exhibit specific electrophysical
properties [1–4]. Much attention has been given recently
to properties of thin films 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 fields
[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 find use in such field of organic electronics
as photovoltonics [4–7].
donor monomers: diphenyl oxide, diphenyl sulfone, and
terphenyl.
EXPERIMENTAL
The starting compounds and solvents were purified
by standard procedures [9–11].
4',4''-Bis(2-carboxybenzoyl)diphenyl sulfide (1) was
synthesized according to [12].
4',4''-Bis(2-carboxybenzoyl)diphenyl sulfone (2).
A 50-mL flask was charged with 1 g of finely ground
4',4''-bis(2-carboxybenzoyl)diphenyl sulfide (1), 20 mL
of 36% hydrogen peroxide, and 10 mL of glacial acetic
acid (or trifluoroacetic 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 final product after the
reaction completion were transferred into distilled water.
The white precipitate was filtered off, washed with three
portions of distilled water, and dried in air at 120°С to
constant weight.
In the first 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 [8]. 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-
The final product, 4',4''-bis(2-carboxybenzoyl)di-
phenyl sulfone (2), was recrystallized two times from
a methanol–water mixture (2 : 1), first in the presence
930

4',4''-BIS(2-CARBOXYBENZOYL)DIPHENYL SULFONE PSEUDODICHLORIDE
931
of activated charcoal and then without it (Тm = 259.5–
261°С). Found, %: С 65.6, Н 3.4, S 6.5. С28Н18О8S.
Calculated, %: С 65.37, Н 3.5. S 6.25.
Photometric determination of 4',4''-bis(2-carb-
oxybenzoyl)diphenyl sulfide. Samples of the reaction
mixture (2–10 mg), taken 1, 2, 3, 5, and 24 h after the
start of the reaction, were dissolved in 50 mL of 96%
sulfuric acid. From the resulting solutions, 1–5-mL
aliquots were taken, transferred into 50-mL volumetric
flasks, and diluted with H2SO4 to the mark. Then,
the colored solutions were subjected to photometric
analysis on a Shimadzu UV-3100 spectrophotometer at
room temperature in a 1-cm quartz cell. The content of
4',4''-bis(2-carboxybenzoyl)diphenyl sulfide n (wt %) in
the reaction mixture was calculated by the formula
c × 105, M
Fig. 1. Optical density D of 4',4''-bis(2-carboxy-benzoyl)
diphenyl sulfide solution in 96% H2SO4 as a function of its
concentration c.
where М1 is the molecular mass of 1; а, sample weight;
ε544, extinction coefficient of 1 at λ = 544 nm; Vt,
H2SO4 volume taken for the dissolution of sample а; V0,
solution volume taken from Vt; V, H2SO4 volume added
for diluting V0; and А544, optical density of the sample
solution in sulfuric acid.
pentachloride was added, and the synthesis was continued
for 10 h. The resulting reaction mass was precipitated into
methanol. The precipitate was washed with methanol and
acetone and dried in air at 120°С for 24 h. The isolated
polymer was subjected to repeated reprecipitation,
washing, and drying.
The quantity ε544 was determined from the calibration
plot shown in Fig. 1, which is described by the linear
equation
The intrinsic viscosity of the polymers obtained was
measured in an Ubbelohde capillary viscometer at 25°С
in tetrachloroethane (TCE).
А544 = 46379[C] – 0.0243 (R = 0.999).
The molecular mass was determined by GPC on
a Waters GPC 2000 liquid chromatograph in THF at
30°С. The values of Mw and Mn were calculated from the
universal calibration dependence for polystyrene.
4',4''-Bis(2-carboxybenzoyl)diphenyl sulfone
pseudodichloride (3). To 5.1 g (0.01 mol) of 4',4''-bis(2-
carboxybenzoyl)diphenyl sulfone, 20 mL of thionyl
chloride was added, and the mixture was refluxed for 6 h.
The precipitate that formed after cooling was filtered off,
washed with thionyl chloride, and vacuum-dried at 100°С
to constant weight (Тm = 172–175°С).
RESULTS AND DISCUSSION
4',4''-Bis(2-carboxybenzoyl)diphenyl sulfide dissolves
in concentrated sulfuric acid to form a solution of intense
dark cherry color (ε544 = 46 380) (Fig. 2, spectrum 1),
whereas 4',4''-bis(2-carboxybenzoyl)diphenyl sulfone
containing a diphenylene sulfone fragment1 is colorless
in H2SO4 (Fig. 2, spectrum 2 and Scheme 1).
Poly(arylene sulfone phthalides) were synthesized
by the following general procedure. A four-necked
flask equipped with a magnetic stirrer, an air condenser,
and a bubble counter was charged in an argon stream
with 0.00076 mol of 4',4''-bis(2-carboxybenzoyl)-
diphenyl sulfone pseudodichloride, 0.00076 mol of the
second monomer, and 0.76 mL of dry, freshly distilled
nitrobenzene. The reaction mixture was heated with
stirring to 100°С, after which 0.00011 mol of antimony
1 Diphenyl sulfone undergoes protonation in concentrated sulfuric
acid but does not undergo ionization and remains colorless [5];
such behavior is rare for organic compounds.
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932
GILEVA et al.
Scheme 1.
Therefore, with the progress of 4',4''-bis(2-carboxy-
composition of the oxidizing mixture and varies within
94–99%. According to the IR data, in all the three cases
the oxidation is selective: The IR spectra of the products
contain characteristic absorption bands of sulfone groups
R–SO2–R' (νas = 1258–1317, νa = 1151–1160 cm–1) and
do not contain absorption bands of sulfoxide groups.
benzoyl)diphenyl sulfide oxidation and enrichment of
the reaction mixture with 4',4''-bis(2-carboxybenzoyl)-
diphenyl sulfone, the color of the sulfuric acid
solutions becomes weaker and fully disappears in 24 h
(Fig. 3). 4',4''-Bis(2-carboxybenzoyl)diphenyl sulfide
is oxidized most rapidly with a mixture of hydrogen
peroxide and trifluoroacetic acid and most slowly with
H2O2/CH3COOH, with the mixture of hydrogen peroxide
and acetic anhydride occupying an intermediate position
(Fig. 4). The conversion of 4',4''-bis(2-carboxybenzoyl)-
diphenyl sulfide is not significantly influenced by the
By refluxing with thionyl chloride, compound 2
was converted into pseudodichloride 3, which was then
used as monomer in polycondensation with terphenyl,
diphenyl sulfide, and diphenyl oxide by the electrophilic
substitution mechanism (Scheme 2).
Scheme 2.
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4',4''-BIS(2-CARBOXYBENZOYL)DIPHENYL SULFONE PSEUDODICHLORIDE
933
λ, nm
λ, nm
Fig. 3. UV absorption spectra of concentration-normalized
(4.66 × 10–5 M) sulfuric acid solutions of the reaction mixture
after oxidation with a mixture of hydrogen peroxide and
trifluoroacetic acid. (1) Mixture before oxidation; oxidation
time, h: (2) 0.5, (3) 1.0, (4) 2.0, (5) 4.0, (6) 8.0, and (7) 24.
Fig. 2. UVabsorption spectra of (1) 4',4''-bis(2-carboxybenzoyl)-
diphenyl sulfide and (2) 4',4''-bis(2-carboxybenzoyl)diphenyl
sulfone in 96% H2SO4. (D) Optical density and (λ) wavelength;
the same for Fig. 3.
n, wt %
In all the three cases, the polycondensation was
performed in nitrobenzene under the conditions
optimum for the majority of polyarylenephthalides
[2]: 100°С, concentration of the monomers 1 M,
catalyst (SbCl5) concentration 15 mol %, 10 h. The
molecular mass of the poly(arylene sulfone phthalides)
formed correlates with the reactivity of the aromatic
hydrocarbons (Table 1), which increases in the order
terphenyl < diphenyl sulfide < diphenyl oxide [13].
Poly(arylene sulfone phthalides) РI—РIII are readily
soluble in a wide range of organic solvents (Table 2)
and in concentrated sulfuric acid and exhibit high heat
resistance (decomposition onset temperature in air and
in an inert medium 450°С).
τ, h
Fig. 4. Kinetic curves of 4',''bis(2-carboxybenzoyl)diphenyl
sulfide oxidation with mixtures of hydrogen peroxide with
(1) acetic acid, (2) acetic anhydride, and (3) trifluoroacetic acid.
(n) Relative content of 4',4''-bis(2-carboxybenzoyl)diphenyl
sulfide and (τ) oxidation time.
CONCLUSIONS
(1) A procedure was developed for heterophase
oxidation of 4',4''-bis(2-carboxybenzoyl)diphenyl
sulfide with peroxy acids using as oxidant a mixture
of hydrogen peroxide with acetic acid, trifluoroacetic
acid, or acetic anhydride. This procedure ensures the
formation of 4',4''-bis(2-carboxybenzoyl)diphenyl sulfone
in quantitative yield.
Table 1. Molecular-mass characteristics of poly(arylene
sulfone phthalides)
Polymer [η], dL g–1 (TCE)
Mn
Mw
РI
РII
РIII
0.15
0.32
0.37
5500
12200
15700
7800
22900
38300
(2) The pseudodichloride formed by halogenation of
4',4''-bis(2-carboxybenzoyl)diphenyl sulfone can be used
as monomer in the synthesis of new polyarylenephthalides
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934
GILEVA et al.
Table 2. Solubility of poly(arylene sulfone phthalides)a
Polymer
РI
Chloroform Dichloroethane Tetrachloroethane Dimethylformamide Cyclohexanone Nitrobenzene
s
s
s*
s
s
s*
s
s
s
s
РII
s
s
PIII
s
s
s
s
s
s
a (s) Dissolves at room temperature and (s*) dissolves on heating.
7. Akkuratov, A.V. and Troshin, P.A., Polym. Sci., Ser. B,
via polycondensation by the electrophilic substitution
mechanism.
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8. Haines, A.H., Methods for the Oxidation of Organic
Compounds, London: Academic, 1988.
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