Synthesis of bis(4-hydroxyphenyl) selenide and epoxide and acrylate monomers on this basis

Article abstract of DOI:10.1134/S1070428015020104

Reaction of SeCl₂ with PhOH has afforded bis(4-hydroxyphenyl) selenide, whose treatment with epichlorohydrin provides a diepoxide that is transformed in bisacrylate and further in tetraacrylate via opening of the epoxide rings with acrylic acid followed by acylation with acryloyl chloride.

Full text of DOI:10.1134/S1070428015020104

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 2, pp. 198–201. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © S.V. Balina, V.V. Russkikh, N.A. Orlova, L.N. Ogneva, V.V. Shelkovnikov, 2015, published in Zhurnal Organicheskoi Khimii, 2015,
Vol. 51, No. 2, pp. 210–213.
Synthesis of Bis(4-hydroxyphenyl) Selenide and Epoxide and
Acrylate Monomers on This Basis
S. V. Balina, V. V. Russkikh, N. A. Orlova, L. N. Ogneva, and V. V. Shelkovnikov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
е-mail: balina@nioch.nsc.ru
Received October 24, 2014
Abstract―Reaction of SeCl2 with PhOH has afforded bis(4-hydroxyphenyl) selenide, whose treatment with
epichlorohydrin provides a diepoxide that is transformed in bisacrylate and further in tetraacrylate via opening
of the epoxide rings with acrylic acid followed by acylation with acryloyl chloride.
DOI: 10.1134/S1070428015020104
The production of polymers transparent in the
visible range and characterized by a high refraction
index is an important task due to their application for
coating optic fibers and other optic elements [1]. One
among the ways to increase the refraction index of a
polymer is the introduction of highly polarizable
atoms, e.g., selenium atoms, into the structure of the
initial monomer [2]. As a synthetic block in the prepa-
ration of organoselenium materials capable of thermal
or photopolymerization bis(4-hydroxyphenyl) selenide
1 may be used with the subsequent functionalization of
the hydroxy groups.
ration of selenide 1 was described under the action on
phenol of the electrophilic cation Se2+ [9]; the
generation of Se2+ was performed electrochemically on
a soluble graphite-selenium anode. Compound 1 was
obtained in 58% yield by the reaction of elemental
selenium with 4-iodophenol in the presence of Cu2O
[10]. The reaction was carried out with adding a ligand
(ethylenediamine) in a system DMSO–KOH at 120°С
under microwave irradiation.
Selenium dichloride SeCl2 seems a promising
reagent for the preparation of selenides, since it can be
successfully used in reactions of electrophilic aromatic
substitution [11, 12], but the best results are obtained
in the synthesis of selenides from phenols substituted
in the ring or their derivatives with the protected
phenol groups. 2,6-Dimethylphenol reacts with SeCl2
giving bis(4-hydroxy-3,5-dimethylphenyl) selenide in
62% yield [11, 12]. Bis(4-methoxyphenyl) selenide 2
was obtained by reacting SeCl2 with anisole in an yield
over 90% demonstrating a high regioselectivity of the
process occurring with replacement of the hydrogen
atom exclusively in the para-position of the phenyl
groups. However, the preparation of selenide 1 from
compound 2 requires an additional stage of removing
the methyl group. Our attempts to perform the
acidolysis of compound 2 by known methods [13, 14]
using HI, Py·HCl failed. The application of HI at a
temperature higher than 60°C resulted in the cleavage
of the Se–C bond and in the formation of selenium,
anisole, and bis(4-methoxyphenyl) diselenide. At the
use of Py·HCl at 185–210°C along with compound 1
The development of a preparative procedure for the
synthesis of compound 1 interested chemists already
for a long time [3]. Two-step syntheses of bis(4-
hydroxyphenyl) selenide 1 were described consisting
in phenol reaction with electrophilic regents (SeOCl2
[3], H2SeO3 [4], SeCl4 [5]) followed by the reduction
of the primarily formed bis(4-hydroxyphenyl)-
selenoxide or dichloride. A multistage synthesis of
compound 1 is also known proceeding from 4-
aminophenol and involving a diazotization stage; the
reaction is accompanied with diselenide formation [6–
8]. Our attempts to obtain selenide 1 with the use of
some among these procedures showed their low
efficiency, irreproducibility, and low yield of the target
compound.
Recently considering the growing interest to
selenium derivatives the search for new reagents for
their synthesis activated. Lately a one-stage prepa-
198

SYNTHESIS OF BIS(4-HYDROXYPHENYL) SELENIDE AND EPOXIDE
199
Scheme 1.
HO
OH
HI
MeO
OMe
SO2Cl2
CHCl3
PhOH
Et2O
Se
SeCl2
Se
Se
1
2
formed also selenium, phenol, and bis(4-hydroxy-
phenyl)diselenide (Scheme 1).
compound 4 with acryloyl chloride provided tetra-
acrylate 5.
The structure of compounds 3–5 was established
based on 1Н NMR and high resolution mass spectra.
In this report, we describe the procedure for
preparation of diaryl selenides by reaction of SeCl2
with arenes modified as compared with the method
[11, 12] by using as a solvent a mixture of chloroform
and ethyl ether. Phenol is brought into the reaction as a
solution in Et2O, the reaction mixture is neutralized
with a water solution of Na2CO3, and unreacted phenol
is distilled off in a vacuum.
Thus in the study a simple method was developed
of the preparation of practically important synthetic
block bis(4-hydroxyphenyl) selenide 1 and proceeding
from the latter a synthesis was fulfilled of epoxide and
acrylate monomers.
EXPERIMENTAL
Thus obtained bis(4-hydroxyphenyl) selenide 1
we used for the preparation of epoxide 3 and
acrylate 4 and 5 monomers (Scheme 2). The sulfide
analog of compound 3 described in patent [15] was
produced in inert medium with the use of sodium
hydride. We applied to the preparation of diglycidyl
ether 3 a simpler procedure described in [16] for
phenol derivative. Bis(4-glycidyloxyphenyl) selenide
3 was converted in bisacrylate 4 by the opening of
the epoxy rings with acrylic acid by procedure
[17]. The subsequent acylation of hydroxy groups in
NMR spectra were registered from solution in
(CD3)2CO for compound 1 and in CDCl3 for
compounds 3–5 on spectrometers Bruker AV-400,
AV-300 and AV-600, operating frequencies 400.13
(1H, internal reference the residual protons of solvents,
δ 2.04 and 7.24 ppm), 75.47 (13C, internal reference
Me2CO, δ 29.8 ppm), and 114.53 MHz (77Se, reference
Me2Se, δ 0 ppm). Mass spectra were taken on an
instrument DFS at direct admission of the sample,
ionizing electrons energy 70 eV, ion source tempe-
Scheme 2.
O
O
O
O
Cl
2
O
1
NaOH aq.
Se
3
Se
O
2CH2=CHCOOH
O
_
BzEt3N+Cl ,
O
O
O
O
90oC, 3 h
4
OH
OH
Se
O
O
2 CH2=CHCOCl
Et3N, CH2Cl2
O
O
O
O
O
O
O
O
5
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015

BALINA et al.
200
rature 180°C. The molecular mass and elemental
composition of compounds 1, 3, and 5 was determined
from the precise values of molecular ion masses. GC-
MS analysis was carried out on an instrument of
Aglient Technologies.
According to GC-MS data the methanol and
chloroform solutions contained compound 1 (9.7,
3.6%), phenol (17.6, 24.6%), initial selenide 2 (6.1,
26.6%), and bis(4-hydroxy-phenyl) diselenide (0 and
1.1% respectively).
4-(4-Hydroxyphenylselanyl)phenol [bis(4-hydro-
xyphenyl) selenide] (1). To a mixture of 0.79 g
(0.01 mol) of selenium and 20 mL of chloroform was
added a solution of 1.35 g (0.01 mol) of sulfuryl
chloride in 20 mL of chloroform, and the mixture was
stirred till selenium was completely dissolved. To the
obtained solution 1.88 g (0.02 mol) of phenol in 20 mL
of anhydrous ethyl ether was added, and the mixture
was stirred at 25°C for 3 h, then a solution of 1.06 g of
Na2CO3 in 4 mL of water was added dropwise, and the
stirring was continued for 10 min till the end of CO2
liberation. The bottom organic layer was separated
from the upper water layer. The former was filtered
through a bed of aluminum oxide (10 cm), the filtrate
was evaporated on a water bath, the residue was
diluted with 5 mL of acetone, and the formed selenium
precipitate was filtered off. Acetone was distilled off
from the filtrate, unreacted phenol was distilled off in a
vacuum, the residue was recrystallized from
chloroform. Yield 1.17 g (44%), mp 143–144°C (mp
Bis[4-(oxiran-2-ylmethoxy)phenyl]selane (3). In
0.93 g (10 mmol) of epichlorohydrin was dissolved
1.33 g (5 mmol) of compound 1, and to the mixture
was added dropwise at vigorous stirring 1.33 g (5 mmol)
of 30% water solution of NaOH. The reaction mixture
was heated while stirring at 70°С for 6 h till the pH of
the medium reached 7, the mixture was cooled to room
temperature, the reaction products were extracted into
dichloromethane (3 × 10 mL). The extract was dried
with CaCl2, the solvent was distilled off, the residue
was chromatographed on a column packed with silica
gel (eluent CH2Cl2), collecting the fraction with Rf
0.21 (eluent CHCl3). After distilling off the eluent the
residue (yellow oily substance) was dried in a vacuum.
1
Yield 1.29 g (69%). H NMR spectrum, δ, ppm: 2.72
d.d (2H, CH2OPh, J1 5.0, J2 2.6 Hz), 2.88 d.d (2H,
CH2OPh, J1 5.0, J2 4.2 Hz), 3.32 m (2H, CHepoxy), 3.89
d.d (2H, CH2Oepoxy, J1 11.2, J2 5.7 Hz), 4.18 d.d (2H,
CH2Oepoxy, J1 11.2, J2 3.1 Hz), 6.81 d (4HAr, J 8.8 Hz),
7.36 d (4HAr, J 8.8 Hz). Found [M]+ 376.0368.
С18Н18О478Se. Calculated M 376.0373.
1
144°C [2], 143−144°C [5]). H NMR spectrum, δ,
ppm: 6.81 d (4HAr, J 8.8 Hz), 7.34 d (4HAr, J 8.8 Hz),
8.60 s (2H, OH). 13C NMR spectrum, δ, ppm: 117.49
(C3), 121.49 (C1), 135.76 (C2), 158.29 (C4). 77Se NMR
spectrum, δ, ppm: 380.74. Found [M]+ 261.9863.
C12H10O276Se. Calculated M 261.9865.
2-Hydroxy-3-[4-({4-[2-hydroxy-3-(prop-2-enoyl-
oxy)propyloxy]phenyl}selanyl)phenoxy]propyl-
prop-2-enoate (4). A mixture of 2.0 g (5.3 mmol) of
diepoxide 3, 0.9 mL (13 mmol) of acrylic acid, and
0.025 g (0.11 mmol) of triethylbenzylammonium
chloride was heated while stirring at 90°С for 3 h. On
cooling the reaction mixture was diluted with 50 mL of
CH2Cl2, the organic layer was washed with water till
рН 7, dried with CaCl2, the solvent was distilled off on
a rotary evaporator. The residue, 2.1 g of colorless oily
Bis(4-methoxyphenyl) selenide (2) was obtained
by procedure [9], mp 54−55°C.
Acidolysis of compound (2). а. To a solution of
0.29 g (1 mmol) of compound 2 in 5 mL of CHCl3 was
added at stirring 3 mL of HI (54% water solution), the
mixture was heated at 60°C and kept for 6 h.
Chloroform solution was separated from water layer
and filtered. We isolated 17 mg (22%) of selenium.
According to GC-MS data the chloroform solution
1
substance containing by Н NMR data 75% of com-
pound 4, was without preliminary purification entered
1
into the next stage. Yield 1.58 g (58%) (by Н NMR
1
data). Н NMR spectrum, δ, ppm: 3.14 d (1Н, ОН, J
5.1 Hz), 3.96 m (2Н, СН2), 4.21 m (1Н, СН), 4.30 m
(2Н, С6Н4ОСН2); 5.82 (HА), 6.11 (HВ), 6.39 (HС)
(АВС system, JАВ 10.4, JАС 1.3, JВС 17.3Hz), protons of
acryloyl groups, 6.76 m (2НAr), 7.33 m (2НAr).
contained anisole (41.3%), initial compound
(21.4%), and bis(4-methoxyphenyl) diselenide (34%).
2
b. A mixture of 0.29 g (1 mmol) of compound 2
and 1.16 g (10 mmol) of Py·HCl was heated at 200°C
for 50 min. The melt was cooled and diluted with 10 mL
of water, the precipitate was filtered off, washed with
5 mL of methanol, and dried in air to obtain 13 mg
(16%) of selenium. From the filtrate the reaction
products were extracted with 20 mL of CHCl3.
1-[4-({4-[2,3-Bis(prop-2-enoyloxy)propoxy]-phe-
nyl}selanyl)phenoxy]-3-(prop-2-enoyloxy)-propan-
2-yl prop-2-enoate (5). To a solution of 2.1 g of the
compound isolated in the previous experiment and
containing 1.58 g (3 mmol) of bisacrylate 4 in 10 mL
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015

SYNTHESIS OF BIS(4-HYDROXYPHENYL) SELENIDE AND EPOXIDE
201
4. Takamatsu, M., J. Pharm. Soc. Jpn., 1928, vol. 48,
of CH2Cl2 was added 2.2 mL (1.6 g, 16 mmol) of
triethylamine, the mixture was cooled on an ice bath at
2 to 5°С and a solution of 1.0 mL (1.11 g, 12 mmol) of
acryloyl chloride in 5 mL of CH2Cl2 was added
dropwise at stirring. The cold bath was removed, the
reaction mixture was stirred at room temperature for 4 h,
diluted with 20 mL of CH2Cl2, washed with water (3 ×
50 mL), dried with CaCl2, the solvent was distilled off
in a vacuum without heating. The viscous oily residue
(2.7 g) was dissolved in benzene and chromatographed
on a column packed with silica gel (50–160 µm),
eluents benzene (fraction 1) and dichloromethane
(fraction 2). Eluent was distilled off in a vacuum from
fraction 2 to obtain 0.9 g (52%) of light yellow oily
tetraacrylate 5. 1Н NMR spectrum, δ, ppm: 4.13 d (2Н,
СН2, J 5.2 Hz), 4.43 d.d (1Н, СН2, J1 12.0, J2 6.1 Hz),
4.51 d.d (1Н, СН2, J1 12.0, J2 4.0 Hz); 5.84 (HА), 6.09
(HВ), 6.39 (HС) (АВС system, JАВ 10.4, JАС 1.3, JВС
17.3 Hz), 5.86 (НА), 6.14 (НВ), 6.44 (НС) (АВС system,
p. 450.
5. Jacob, C., Giles, G., and Fry, F., WO Patent no.
2004047925, 2004; Chem. Abstr., 2004, vol. 141,
no. 17656.
6. Keimatsu, S. and Yokota, K., J. Pharm. Soc. Jpn., 1932,
vol. 52, p. 19.
7. Matti, J., Bull. Soc. Chim., 1940, vol. 7, p. 617.
8. Keimatsu, S. and Yokota, K., J. Pharm. Soc. Jpn., 1930,
vol. 50, p. 79.
9. Guillanton, G., Quang, T., Elothmani, D., and Simonet, J.,
France Patent no. 2665714, 1992; Chem. Abstr., 1993,
vol. 118, no. 13271u.
10. Zhang, S., Karra, K., Heintz, C., Kleckler, E., and Jin, J.,
Tetrahedron Lett., 2013, vol. 54, p. 4753.
11. Potapov, V.A., Khuriganova, O.I., and Amosova, S.V.,
Russ. J. Org. Chem., 2009, vol. 45, p. 1569.
12. Khuriganova, O.I., Candidate Sci. (Chem.) Dissertation,
Irkutsk, 2010.
13. Wuts, P.J.M. and Greene, T.W., Greene’s Protective
Groups in Organic Synthesis, New York etc: J. Wiley &
Sons Inc., 2007.
14. Zashchitnye gruppy v organicheskoi khimii (Protection
Groups in Organic Chemistry), McOmi, J., Ed.,
Moscow: Mir, 1976.
J
АВ 0.4, JАС 1.3, JВС 17.3 Hz) – protons of two acryloyl
groups, 6.80 m (2НAr), 7.37 m (2НAr). Found [M]+
628.1007. C30H30O1078Se. Calculated M 628.1008.
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