VELIKORODOV et al.
1888
refluxed for 2 h. The mixture was cooled, and the
crystalline solid was filtered off, washed on a filter with
25 mL of propan-2-ol, dried in air, and recrystallized
from ethanol. Yield 0.72 g (96%), colorless crystals,
mp 197–198°C [4]. Found, %: C 52.11; H 3.88;
N 15.28. C12H11N3O3S. Calculated, %: C 51.99;
H 3.97; N 15.16.
4.0 Hz), 6.28 s (1H, NH), 6.47–7.60 m (3H, Harom),
8.21 d (2H, Harom, J = 8.7 Hz), 7.90 d (2H, Harom
,
J = 8.7 Hz), 11.82 s (1H, NH), 13.83 s (1H, OH).
13C NMR spectrum, δC, ppm: 34.9 (C3), 66.0 (C2), 97.2
(C5′); 115.9, 120.5, 121.2, 123.2, 123.5, 125.5, 125.9,
128.7, 132.8, 139.3, 147.1, 141.2, 147.3 (Carom); 162.7
and 169.7 (C6′, C2′), 167.8 (C4′), 181.3 (C4). Found, %:
C 58.11; H 3.18; N 11.54.C23H16N4O6S. Calculated, %:
C 57.98; H 3.36; N 11.77.
5-{2-[5-(4-Bromophenyl)furan-2-yl]-2,3-dihy-
dro-1H-1,5-benzodiazepin-4-yl}-4-hydroxy-2H-
1,3-thiazine-2,6(3H)-dione (11) was synthesized
according to the procedure described above for the
synthesis of 8 from 0.5 g (2.67 mmol) of 1, 0.288 g
(2.67 mmol) of o-phenylenediamine, and 1.34 g
(5.34 mmol) of 5-(4-bromophenyl)furan-2-carbalde-
hyde (9). Yield 1.2 g (85%), colorless crystals,
mp 223–226°C (from dioxane; the product was then
dried for 6 h under reduced pressure). IR spectrum,
ν, cm–1: 3360 (NH), 3250 (OH), 1668 (C=O), 1632
5-{(E)-3-[5-(4-Bromophenyl)furan-2-yl]prop-
2-enoyl}-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione
(13). A mixture of 0.5 g (2.67 mmol) of thiazine 1,
0.65 g (2.78 mmol) of aldehyde 9, 5 drops of pyridine,
and 5 drops of piperidine in 15 mL of chloroform was
refluxed for 2 h. The mixture was cooled, and the red
solid was filtered off, washed with diethyl ether, dried
in air, and recrystallized from ethanol. Yield 1 g (90%),
red crystals, mp 210–212°C. IR spectrum, ν, cm–1: 3280
(NH), 3148 (OH), 1680 (C=O), 1610, 1570 (C=Carom).
1H NMR spectrum, δ, ppm: 6.49 d (1H, HFu, J =
3.6 Hz), 6.60 d (1H, HFu, J = 3.6 Hz), 6.81 d (1H,
HC=CH, J = 15.7 Hz), 7.32 d (2H, Harom, J = 8.5 Hz),
7.43 d (2H, Harom, J = 8.5 Hz), 7.75 d (1H, HC=CH,
J = 15.7 Hz), 11.52 (NH), 12.54 (OH). Found, %:
C 48.21; H 2.15; N 3.09. C17H10BrNO5S. Calculated,
%: C 48.57; H 2.38; N 3.33.
1
(C=N), 1591, 1567 (C=Carom). H NMR spectrum, δ,
ppm: 2.98 d.d (1H, JAB = 12.5, JAX = 10.4 Hz), 3.75 d.d
(1H, JAB = 12.5, JBX = 2.4 Hz), and 5.15 d.d (1H, JAX
=
10.5, JBX = 2.4 Hz) (CH2CH); 5.52 d (1H, HFu, J =
4.0 Hz), 6.07 d (1H, Harom, J = 8.0 Hz), 6.19 d (1H, HFu,
J = 4.0 Hz), 6.25 s (1H, NH), 6.47–7.60 m (3H, Harom),
8.17 d (2H, Harom, J = 9.0 Hz), 7.65 d (2H, Harom, J =
9.0 Hz), 11.82 s (1H, NH), 13.83 s (1H, OH). 13C NMR
spectrum, δC, ppm: 35.1 (C3), 64.5 (C2), 97.2 (C5′);
115.9, 120.5, 121.2, 123.2, 123.5, 125.0, 126.0, 128.7,
132.8, 139.3, 141.0, 141.2, 141.9 (Carom); 162.7 and
169.7 (C6′, C2′), 167.7 (C4′), 181.3 (C4). Mass spectrum,
m/z (Irel, %): 511 (78.9) [M + 1]+, 510 (84.5), 478 (11),
451 (34), 450 (24), 367 (38), 363 (22.5), 340 (77.5),
262 (48.6), 248 (54), 235 (33.8), 193 (33), 182 (47),
144 (30), 133 (64.8), 128 (33), 103 (30), 77 (21.8),
60 (57), 44 (70), 32 (100). Found, %: C 54.10; H 3.00;
N 7.99. C23H16BrN3O4S. Calculated, %: C 54.12;
H 3.14; N 8.24. M 510.
4-Hydroxy-5-{(E)-3-[5-(4-nitrophenyl)furan-
2-yl]prop-2-enoyl}-2H-1,3-thiazine-2,6(3H)-dione
(14) was synthesized in a similar way from 0.5 g
(2.67 mmol) of 1 and 0.60 g (2.78 mmol) of 10. Yield
0.9 g (87%), yellow–orange crystals, mp 254–256°C
(from EtOH). IR spectrum, ν, cm–1: 3287 (NH), 3152
(OH), 1680 (C=O), 1610, 1570 (C=Carom), 1525 (NO2,
asym.), 1340 (NO2, sym.). 1H NMR spectrum, δ, ppm:
6.54 d (1H, HFu, J = 3.7 Hz), 6.77 d (1H, HC=CH,
J = 15.8 Hz), 6.84 d (1H, HFu, J = 3.7 Hz), 7.62 d (1H,
HC=CH, J = 15.8 Hz), 7.80 d (2H, Harom, J = 8.6 Hz),
8.08 d (2H, Harom, J = 8.6 Hz), 11.22 (NH), 12.62 (OH).
Found, %: C 52.59; H 2.34; N 6.95. C17H10N2O7S.
Calculated, %: C 52.85; H 2.59; N 7.25.
4-Hydroxy-5-{2-[5-(4-nitrophenyl)furan-2-
yl]-2,3-dihydro-1H-1,5-benzodiazepin-4-yl}-2H-
1,3-thiazine-2,6(3H)-dione (12) was synthesized in
a similar way from 0.5 g (2.67 mmol) of 1, 0.288 g
(2.67 mmol) of o-phenylenediamine, and 1.16 g
(5.34 mmol) of 5-(4-nitrophenyl)furan-2-carbaldehyde
(10). Yield 1.1 g (86%), yellow crystals, mp 231–233°C
(from EtOH). IR spectrum, ν, cm–1: 3368 (NH), 3252
(OH), 1680 (C=O), 1635 (C=N), 1590, 1565 (C=Carom),
1515, 1350 (NO2). 1H NMR spectrum, δ, ppm: 2.97 d.d
FUNDING
This study was performed under financial support by the
Ministry of Science and Higher Education of the Russian
Federation (project no. 4.9288.2017BCh) and by the Russian
Foundation for Basic Research (project no. 19-03-00006 A).
(1H, JAB = 12.5, JAX = 10.4 Hz), 3.73 d.d (1H, JAB
=
12.4, JBX = 2.4 Hz), and 5.15 d.d (1H, JAX = 10.5,
JBX = 2.4 Hz) (CH2CH); 5.55 d (1H, HFu, J = 4 Hz),
6.05 d (1H, Harom, J = 8.0 Hz), 6.20 d (1H, HFu, J =
CONFLICT OF INTERESTS
The authors declare the absence of conflict of interests.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019