Synthesis of benzene-1,4-diylbis(oxyethane-2,1-diyl) bis[(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)benzoates]

Full text of DOI:10.1134/S1070428015060159

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 6, pp. 901–902. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © O.A. Kolyamshin, M.V. Kuz’min, V.A. Ignat’ev, L.G. Rogozhina, N.I. Kol’tsov, 2015, published in Zhurnal Organicheskoi Khimii,
2015, Vol. 51, No. 6, pp. 917–918.
SHORT
COMMUNICATIONS
Synthesis of Benzene-1,4-diylbis(oxyethane-2,1-diyl)
Bis[(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)benzoates]
O. A. Kolyamshin, M. V. Kuz’min, V. A. Ignat’ev, L. G. Rogozhina, and N. I. Kol’tsov
I.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: oleg.kolyamshin@yandex.ru
Received July 8, 2014
DOI: 10.1134/S1070428015060159
Maleimides and their derivatives are important
monomers for the preparation of various thermo-
plastics and composites which sometimes exceed
epoxy composites in such characteristics as heat resis-
tance and mechanical strength. Therefore, the use of
these materials is very promising, especially in high-
technology fields: astronautics, automobile industry,
aircraft construction, electronics, and electrotechnics
[1, 2]. Some maleimide derivatives are used as
pesticides; they show high insecticidal, fungicidal, and
herbicidal activity [3–5]. Maleimides have been pro-
posed as highly efficient pharmaceutical agents for the
treatment of a number of diseases, including cardio-
vascular disorders, Alzheimer disease, type II diabetes,
cancer, and AIDS [6–8]. Taking into account the above
stated, both synthesis of new maleimides and polymers
based thereon and exploration of new fields of applica-
tion of already known maleimides are topical prob-
lems. We previously synthesized various maleimides
and their derivatives [9–12]. In the present communi-
cation we describe the synthesis of new bis-malei-
mides containing an alkylaromatic moiety and their
physical and spectral properties.
By heating 3- and 4-maleinimidobenzoic acids 1a
and 1b [13] in thionyl chloride according to modified
procedure [14] we obtained light yellow solid acid
chlorides 2a and 2b which were reacted with 1,4-bis-
(2-hydroxyethoxy)benzene in benzene in the presence
of triethylamine as hydrogen chloride acceptor. As
a result, we isolated light yellow crystalline bis-male-
imides 3a and 3b containing alkylaromatic groups.
The purity of compounds 3a and 3b was checked
by TLC, and their structure was confirmed by elemen-
tal analyses and IR and 1H NMR spectra. The IR spec-
tra of 3a and 3b contained a weak but characteristic
absorption band at 3080–3100 cm–1 due to stretching
vibrations of C–H bonds in the CH=CH fragments, and
stretching vibrations of the carbonyl groups appeared
as several strong bands in the region 1700–1720 cm–1.
Protons in the maleimide rings of 3a and 3b gave rise
to a singlet at δ 7.20–7.22 ppm in the 1H NMR spectra.
O
O
SOCl2
N
N
COOH
COCl
O
O
1a, 1b
2a, 2b
O
O
O
4-HOCH2CH2OC6H4OCH2CH2OH
2Et3N
O
O
N
N
–2Et3N· HCl
O
O
O
O
O
3a, 3b
para Isomer (a), meta isomer (b).
901

KOLYAMSHIN et al.
902
The IR spectra were recorded on a Specord 75 IR
4-(2,5-Dioxo-2,5-dihydro-1H-pyrrol-1-yl)benzoyl
spectrometer from samples dispersed in mineral oil.
chloride (2a). A mixture of 8.68 g (0.04 mol) of acid
1a, 9.52 g (0.08 mol) of thionyl chloride, 5 drops of
DMF, and 150 mL of benzene was heated for 2 h under
reflux. The slightly turbid solution was filtered while
hot through a folded filter paper, and the light yellow
filtrate was evaporated under reduced pressure (water-
jet pump) on heating on a water bath. Yield 8.03 g
(85%), light yellow powder, mp 165–167°C; published
data [14]: mp 167.7–168.5°C. IR spectrum, ν, cm–1:
3085 (=C–H), 1705 (C=O), 890 (C–Cl), 3040, 1595,
820 (C–Harom), 890 (C–Cl).
1
The H NMR spectra were measured on a Bruker
DRX-500 spectrometer at 500.13 MHz using
DMSO-d6 as solvent and tetramethylsilane as internal
reference. Analytical TLC was performed on Sorbfil
PTSKh-P-V plates using ethanol–hexane (3 :1) as
eluent; spots were visualized by treatment with iodine
vapor. The elemental compositions were determined
on a Perkin Elmer 2400 CHN analyzer.
This study was performed in the framework of the
base part of a state contract of the Ministry of Educa-
tion and Science of the Russian Federation.
3-(2,5-Dioxo-2,5-dihydro-1H-pyrrol-1-yl)benzoyl
chloride (2b) was synthesized in a similar way.
Yield 82%, light yellow powder, mp 130–131°C.
IR spectrum, ν, cm–1: 1695 (C=O), 890 (C–Cl), 1595,
840 (C–Harom).
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Benzene-1,4-diylbis(oxyethane-2,1-diyl)
bis[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)ben-
zoate] (3a). Acid chloride 2a, 4.71 g (0.02 mol), was
gradually added under stirring to a mixture of 1.98 g
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2.02 g (0.02 mol) of triethylamine in 50 mL of
benzene, and the mixture was stirred for 2 h at room
temperature and for 2 h at 55°C. The precipitate of tri-
ethylamine hydrochloride was filtered off, the filtrate
was evaporated under reduced pressure (water-jet
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mp 94–96°C (from acetone), Rf 0.76. IR spectrum, ν,
cm–1: 3080 (=C–H), 1720, 1705 (C=O), 1275
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1
(C–O–C), 3050, 1600, 825 (C–Harom). H NMR spec-
trum, δ, ppm: 4.29 t (4H, CH2O, 3J = 4 Hz), 4.59 t [4H,
3
CH2OC(O), J = 4 Hz], 6.94 s (4H, C6H43), 7.22 s (4H,
CH=CH), 7.54 d and 8.06 d (8H, C6H4, JHH = 8 Hz).
Found, %: C 64.43; H 4.06; N 4.70. C32H24N2O10. Cal-
culated, %: C 64.21; H 4.11; N 4.59.
Benzene-1,4-diylbis(oxyethane-2,1-diyl)
bis[3-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)ben-
zoate] (3b) was synthesized in a similar way. Yield
72%, light yellow powder, mp 141–142°C (from
acetone, double crystallization), Rf 0.82. IR spectrum,
ν, cm–1: 3100, 1610 (CH=CH), 1720, 1700 (C=O),
1290 (C–O–C), 3050, 1590, 830, 700 (C–Ha3rom).
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3
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(4H, C6H4), 7.20 s (4H, CH=CH), 7.65 m and 7.96 m
(8H, C6H4). Found, %: C 64.43; H 4.06; N 4.70.
C32H24N2O10. Calculated, %: C 64.32; H 4.10; N 4.65.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 6 2015