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New Journal of Chemistry
Page 8 of 10
DOI: 10.1039/C7NJ03846A
ARTICLE
Journal Name
Brown solid, yield 70%; mp 300 °C; IR (KBr, cm-1) νmax 3420,
3350 (N–H), 2216 (CN), 1601, 1513 (NO2), 1330, 1128 (O=S=O);
1Н NMR (500 MHz, DMSO-d6) δ 3.25 (2H, t, 3J = 6.4 Hz, C(4)H2),
3.38 (2H, t, 3J = 6.4 Hz, C(3)H2), 4.62 (2H, s, C(1)H2), 6.96 (2H, br
s, NH2), 7.20 (1H, d, 3J = 3.6 Hz, H-furyl), 7.56 (1H, d, 3J = 3.6 Hz,
Calcd for C8H8N2O2S: C, 48.97; H, 4.11; N, 14.28 %; Found C, 49.09;
H, 4.32; N, 14.09 %.
General procedure for the synthesis of 7-amino-5-aryl-3,4-
dihydro-1H-isothiochromene-6,8-dicarbonitrile-2,2-dioxides 5a-i
Тo a solution of the corresponding aldehyde ArCHO (2.4 mmol) in
15 mL of EtOH, ketosulfone 1 (350 mg, 2.4 mmol), malononitrile
(320 mg, 4.8 mmol) and 2 drops of piperidine were added in
succession. The mixture was heated under reflux for 5 h and then
allowed to cool. The precipitate formed was filtered off, washed
with cold EtOH (10 ml) and purified by recrystallization from EtOH–
DMF (1:1) mixture to give pure final products.
3
H-furyl), 8.05 (2H, d, 3J = 9.0 Hz, H-Ar), 8.32 (2H, d, J = 9.0 Hz,
H-Ar); 13С NMR (126 MHz, DMSO-d6) δ 26.8, 48.3, 53.4, 96.5,
97.6, 112.3, 114.7, 115.8, 117.6, 121.8, 125.0 (2C), 125.1 (2C),
135.6, 137.8, 140.5, 147.0, 148.8, 152.4, 153.1; MS (m/z, APCI)
435.0 [M+H]+; Anal. calcd for C21H14N4O5S: C, 58.06; H, 3.25; N,
12.90 %; Found: C, 58.13; H, 3.34; N, 12.96 %.
7-Amino-5-[5-(2-nitrophenyl)-2-furyl]-3,4-dihydro-1H-
isothiochromene-6,8-dicarbonitrile 2,2-dioxide (5e)
7-Amino-5-phenyl-3,4-dihydro-1H-isothiochromene-6,8-
dicarbonitrile-2,2-dioxide (5а)
Brown solid, yield 76%; mp 246 °C; IR (KBr, cm-1) νmax 3420,
3350 (N–H), 2213 (CN), 1656 (C=C), 1522 (NO2), 1329, 1127
White solid, yield 80%, mp 277 °С; IR (KBr, cm-1) νmax 3418, 3351 (N–
1
3
(O=S=O); Н NMR (500 MHz, DMSO-d6) δ 3.12 (2H, t, J = 6.5
H), 2217 (CN), 1651 (C=C), 1290, 1129 (O=S=O); 1Н NMR (500 MHz,
Hz, C(4)H2), 3.36 (2H, t, 3J = 6.5 Hz, C(3)H2), 4.61 (2H, s, C(1)H2),
3
DMSO-d6
)
δ 2.84 (2H, t, 3J = 6.5 Hz, C(4)H2), 3.29 (2H, t, J = 6.5 Hz,
3
6.96 (2H, s, NH2), 7.14 (1H, d, J = 3.6 Hz, H-furyl), 7.17 (1H, d,
3J = 3.6 Hz, H-furyl), 7.65-7.66 (1H, m, H-Ar), 7.78-7.79 (1H, m,
H-Ar), 7.94–7.98 (2H, m, H-Ar); 13С NMR (126 MHz, DMSO-d6) δ
26.4, 48.4, 53.4, 97.0, 97.8, 112.2, 114.7, 115.6, 116.8, 122.0,
122.4, 124.6, 129.69, 130.5, 133.2, 137.7, 140.4, 147.5, 148.7,
150.3, 152.3; MS (m/z, APCI) 435.0 [M+H]+; Anal. Calcd for
C21H14N4O5S: C, 58.06; H, 3.25; N, 12.90 %; Found: C, 58.11; H,
3.32; N, 12.98 %.
C(3)H2), 4.56 (2H, br s, C(1)H2), 6.72 (2H, br s, NH2), 7.32-7.34 (2H,
m, H-Ar), 7.52-7.56 (3H, m, H-Ar); 13С NMR (126 MHz, DMSO-d6
)
δ
26.2, 48.2, 53.1, 96.0, 97.5, 114. 4, 115.1, 120.9, 128.3 (2С), 128.9
(2С), 129.1, 136.4, 139.1, 150.3, 151.5; MS (m/z, APCI) 324.0
[М+H]+; Anal. Calcd for C17H13N3O2S: C, 63.14; H, 4.05; N, 12.99 %;
Found C, 63.30; H, 3.91; N, 12.80 %.
7-Amino-5-[5-(4-chlorophenyl)-2-furyl]-3,4-dihydro-1H-
isothiochromene-6,8-dicarbonitrile 2,2-dioxide (5b)
Yellow solid, yield 81%, mp 326 °C; IR (KBr, cm-1) νmax 3420, 3352
(N–H), 2217 (CN), 1656 (C=C), 1292, 1144 (O=S=O); 1Н NMR (500
3
MHz, DMSO-d6) δ 3.25 (2H, t, J = 6.4 Hz, C(4)H2), 3.38 (2H, t, J =
7-Amino-5-[5-(4-methyl-2-nitrophenyl)-2-furyl]-3,4-dihydro-
1H-isothiochromene-6,8-dicarbonitrile-2,2-dioxide (5f)
Brown solid, yield 84%; mp 239 °C; IR (KBr, cm-1) νmax 3421,
3357 (N–H), 2216 (CN), 1644 (C=C), 1525 (NO2), 1321, 1124
(O=S=O); 1Н NMR (500 MHz, DMSO-d6) δ 2.43 (3H, s, CH3), 3.12
(2H, t, 3J = 6.5 Hz, C(4)H2), 3.35 (2H, t, 3J = 6.5 Hz, C(3)H2), 4.60
3
6.4 Hz, C(3)H2), 4.61 (2H, s, C(1)H2), 6.92 (2H, br s, NH2), 7.13 (1H, d,
3J = 3.6 Hz, H-furyl), 7.28 (1H, d, 3J = 3.6 Hz, H-furyl), 7.55 (2H, d, 3J =
8.5 Hz, H-Ar), 7.83 (2H, d, 3J = 8.5 Hz, H-Ar); 13С NMR (126 MHz,
3
(2H, s, C(1)H2), 6.94 (2H, br s, NH2), 7.10 (1H, d, J = 3.6 Hz, H-
furyl), 7.12 (1H, d, 3J = 3.7 Hz, H-furyl), 7.60 (1H, dd, J = 8.0, 0.9
Hz, H-Ar), 7.78 (1H, s, H-Ar), 7.84 (1H, d, 3J = 8.0 Hz, H-Ar); 13С
NMR (126 MHz, DMSO-d6) δ 20.9, 26.4, 48.4, 53.42, 96.9, 97.7,
111.6, 114.7, 115.6, 116.8, 119.8, 121.9, 124.6, 129.5, 133.7,
137.8, 140.4, 141.0, 147.4, 148.4, 150.5, 152.3; MS (m/z, APCI)
449.0 [M+H]+; Anal. Calcd for C22H16N4O5S: C, 58.92; H, 3.60; N,
12.49 %; Found: C, 58.99; H, 3.67; N, 12.55 %.
DMSO-d6) δ 26.8, 48.3, 53.4, 96.3, 97.2, 109.1, 114.8, 115.9, 117.4,
121.6, 126.1 (2C), 128.8, 129.6 (2C), 133.4, 138.1, 140.3, 147.1,
152.4, 154.3; MS (m/z, APCI) 424.0 [М+H]+; Anal. Calcd for
C21H14ClN3O3S: C, 59.51; H, 3.33; N, 9.91 %. Found: C, 59.58; H, 3.41;
N, 9.98 %.
7-Amino-5-[5-(2,4-dichlorophenyl)-2-furyl]-3,4-dihydro-1H-
isothiochromene-6,8-dicarbonitrile-2,2-dioxide (5c)
7-Amino-5-[5-(4-bromophenyl)-2-furyl]-3,4-dihydro-1H-
isothiochromene-6,8-dicarbonitrile 2,2-dioxide (5g)
Yellow solid, yield 78%, mp 244 °C (recrystallization gave
solvate 5c · 0.5 DMF); IR (KBr, cm-1) νmax 3340 (N–H), 2213
(CN), 1632 (C=C), 1296, 1129 (O=S=O); 1Н NMR (500 MHz,
DMSO-d6) δ 2.73 (1.5H, s, NCH3 (DMF)), 2.89 (1.5H, s, NCH3
(DMF)), 3.25 (2H, t, 3J = 6.0 Hz, C(4)H2), 3.37 (2H, t, 3J = 6.0 Hz,
C(3)H2), 4.61 (2H, s, C(1)H2), 6.96 (2H, br s, NH2), 7.17-7.18 (1H,
Yellow solid, yield 88%; mp 336 °C; IR (KBr, cm-1) νmax 3423,
3354 (N–H), 2218 (CN), 1657 (C=C), 1566 (NO2), 1291, 1126
1
3
(O=S=O); Н NMR (500 MHz, DMSO-d6) δ 3.25 (2H, t, J = 6.4
Hz, C(4)H2), 3.37 (2H, t, 3J = 6.4 Hz, C(3)H2), 4.60 (2H, s, C(1)H2),
3
6.91 (2H, br s, NH2), 7.12 (1H, d, J = 3.6 Hz, H-furyl), 7.29 (1H,
3
d, 3J = 3.6 Hz, H-furyl), 7.68 (2H, d, J = 8.5 Hz, H-Ar), 7.76 (2H,
3
3
d, J = 2.9 Hz, H-furyl), 7.41 (1H, d, J = 2.9 Hz, H-furyl), 7.59
(1H, d, 3J = 8.4 Hz, H-Ar), 7.80 (1H, s, H-Ar), 7.94–7.96 (1.5H, m,
H-Ar + CHO (DMF) overlapped); MS (m/z, APCI) 458.0 [М+H]+;
d, 3J = 8.5 Hz, H-Ar); 13С NMR (126 MHz, DMSO-d6) δ 26.8, 48.3,
53.4, 96.3, 97.2, 109.1, 114.8, 115.9, 117.4, 121.6, 121.9, 126.4
(2C), 129.1, 132.5 (2C), 138.0, 140.3, 147.2, 152.4, 154.3; MS
(m/z, APCI) 469.0 [M+H]+; Anal. Calcd for C21H14BrN3O3S: C,
53.86; H, 3.01; N, 8.97 %; Found: C, 53.92; H, 3.08; N, 9.02 %.
Anal. Calcd for C21H13Cl2N3O3S · 0.5C3H7NO: C, 55.03; H, 2.86;
N, 9.17 %; Found: C, 55.11; H, 2.94; N, 9.23 %.
7-Amino-5-[5-(4-nitrophenyl)-2-furyl]-3,4-dihydro-1H-
isothiochromene-6,8-dicarbonitrile 2,2-dioxide (5d)
8 | New J. Chem., 2017, 00, 1-10
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