1
688
KOLYMSHIN et al.
{
2-[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)-phenylcar-
8.6 Hz), 10.95 s [2Н, 2С(O)NH]. Found, %: С 64.43;
Н 3.46; N 8.60. C H Сl N O . Calculated, %: С
bonyloxy]ethoxy}benzene (6).
EXPERIMENTAL
3
5
22
2
4
6
6
3.17; Н 3.33; N 8.42.
1
,4-Bis[2-(4-aminophenylcarbonyloxy)ethoxy]-
The IR spectra were measured on a FSM 1202
FTIR spectrometer for thin films of suspensions in
mineral oil. The Н NMR spectra were run on a Bruker
benzene (4). A mixture of 3.50 g (0.02 mol) of potas-
sium p-aminobenzoate, 2.35 g (0.01 mol) of 1,4-bis(2-
chloroethoxy)benzene, 0.1 g of triethylbenzylammo-
nium chloride, and 15 mL of DMF was stirred at 130–
140°С for 4 h. After cooling to room temperature, the
mixture was diluted with 200 mL of water, and stirring
was continued. The precipitate that formed was filtered
off under vacuum, washed with water (5 × 5 mL), and
dried in air. Yield 3.92 g (89.9%), light gray powder,
1
DRX500 spectrometer (500.13 MHz) in DMSO-d6,
internal reference TMS. The elemental analyses were
obtained on a Vario Micro Cube СНN analyzer. The
melting points were measured on an OptiMelt
MPA100 instrument. Reaction progress and purity of
the synthesized compounds were monitored by TLC
on Sorbfil PTSKh-P-V plates (Sorbpolymer, Kras-
nodar, Russia) in 1,4-dioxane; the spots were
visualized by exposure to iodine vapor. Solvents were
used as received. 1,4-Bis(2-chloroethoxy)benzene was
synthesized as described in [16], yield 69%, mp 98–
mp 198–199°С (dioxane). R
cm : 3468, 3376, 3235 (NH
0.65. IR spec-trum, ν,
), 1689, 1635 (C=O),
2
f
–
1
1275 (C–O–C), 1603 (CH=CH), 768 (C–Cl), 1595,
1
825 (Ar–H). Н NMR spectrum, δ, ppm: 4.29 t (4Н,
3
3
2CH
, JНН 4.6 Hz), 4.45 t (4Н, 2CH
, JНН
4.6
2
2
3
1
00°С (toluene).
Hz), 5.98 s (4Н, 2NH
2
), 6.56 d and 7.64 d (8Нarom, JНН
.6 Hz), 6.91 s (8Нarom). Found, %: С 66.15; Н 5.47; N
.30. C H N O . Calculated, %: С 66.05; Н 5.54; N
8
6
6
4
-(2,5-Dioxo-2,5-dihydro-1Н-pyrrol-1-yl)benzoyl
2
4
24
2
6
chloride (2). A mixture of 8.68 g (0.04 mol) of 4-(2,5-
dioxo-2,5-dihydro-1Н-pyrrol-1-yl)benzoic acid (1),
.42.
9
.52 g (0.08 mol) of thionyl chloride, 5 droplets of
1,4-Bis[4-(2-carboxyethen-1-ylcarbamoyl)phe-
DMF, and 150 mL of benzene was heated under reflux
for 2 h with stirring (to avoid strong shocks), and then
filtered, and the light yellow filtrate was evaporated in
a vacuum under heating. Yield 8.03 g (85.2%), light
yellow powder, mp 165–167°С (167.7–168.5°С [15]).
nylcarbonyloxyethoxy]benzene (5). A solution of
0.98 g (10 mmol) of maleic anhydride in 10 mL of
acetone was added to a suspension of 2.18 g (5 mmol)
of diamine 4 in 20 mL of acetone. The thick creamy
material that formed was heated at 50°С for 1 h, the
precipitate was filtered off at room temperature,
washed with acetone (3 × 2 mL), and dried in air. Yield
2.50 g (79.1%), beige powder, mp 191–192°С (acetone).
–
1
IR spectrum, ν, cm : 3085 (СН=СН), 1705 (С=О),
90 (СОСl), 3040, 1595, 820 (Ar–H), 890 (СОСl).
C H ClNO .
8
11
6
3
–
1
R 0.55. IR spectrum, ν, cm : 3306, 3206 [C(O)NH],
f
4,4'-Bis[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)-
1
715 (C=O), 1623 (CH=CH), 1283 (C–O–C), 766 (C–
phenylcarbonylamino]-3,3'-dichlorodiphenylme-
thane (3). Chloride 2, 11.68 g (0.0496 mol), was
added dropwise at room temperature to a stirred
solution of 6.62 g (0.0248 mol) of 4,4'-diamino-3,3'-
dichlorodiphenylmethane and 5.02 g (0.0496 mol) of
triethylamine in 100 mL of benzene. The resulting
mixture was stirred at room temperature for 2 h and at
1
Cl), 3116, 1579, 853 (Ar–H). Н NMR spectrum, δ,
3
ppm: 4.26 t (4Н, 2CH , J 4.6 Hz), 4.55 t (4Н, 2CH ,
2
НН
2
3
3
JНН 4.6 Hz), 6.34 d and 6.49 d (2Н, СН=СН, J
HH
1
2.0 Hz), 6.93 s (4Нarom), 7.76 d and 7.93 d (8Нarom,
3
JНН 8.7 Hz), 10.62 s [2Н, С(O)NH], 12.90 s (2Н,
2
СООН). Found, %: С 60.43; Н 4.61; N 4.37.
C H N O . Calculated, %: С 60.77; Н 4.46; N 4.43.
3
2
28
2
12
5
0°С for 1 h. Triethylamine hydrochloride was filtered
off, the filtrate was evaporated, the residue was
triturated with 300 mL of water, and the precipitate
was filtered off, washed with water (5 × 10 mL) , dried
in air, and recrystallized 2 times from acetone. Yield
1,4-Bis{2-[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-
yl)phenylcarbonyloxy]ethoxy}benzene (6). A mixture
of 1.90 g (0.003 mol) of diamide 5, 1.44 g (0.012 mol)
of acetic anhydride, 0.2 g of calcined sodium acetate in
8 mL of DMF was stirred at 45–65°С for 3 h, after
1
5.33 g (92.9%), mp 202–204°С (acetone). R 0.67. IR
f
–
1
spectrum, ν, cm : 1715, 1680 (С=О), 1606, 824 (Ar–
H). Н NMR spectrum, δ, ppm: 4.01 s (2H, СН ), 7.23 s
which it was diluted with 90 mL water (MgSO was
4
1
2
added to facilitate precipitation of the product), and
stirring was continued. The precipitate was filtered off,
washed with water (5 × 5 mL), and dried in air. Yield
3
(
4Н, 2СН=СН), 7.30 d and 7.31 d (2Нarom, J 1.9 Hz),
НН
3
7
.50–7.56 m (4Нarom), 7.53 d and 8.08 d (8Нarom, JНН
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 11 2019
Kolymshin
