40 JOURNAL OF CHEMICAL RESEARCH 2016
J = 7.8, 1.2 Hz, 1H, ArH), 7.61–7.55 (m, 1H, ArH), 7.47 (d, J = 7.7 Hz,
1H, ArH), 7.43–7.37 (m, 1H, ArH), 7.35–7.27 (m, 2H, ArH), 7.06 (d,
J = 8.1 Hz, 1H, ArH), 6.92 (t, J = 7.5 Hz, 1H, ArH), 5.48 (dd, J = 9.1,
6.2 Hz, 1H, CH), 3.97–3.85 (m, 2H, CH2), 3.84 (s, 3H, OCH3); 13C NMR
(DMSO-d6, 100 MHz): δ 156.7 (C=O), 152.9 (ArH), 152.6 (ArH),
147.7 (C=C–S), 130.9 (ArH), 129.7 (ArH), 129.6 (ArH), 127.0 (ArH),
126.8 (ArH), 125.6 (ArH), 125.4 (ArH), 121.1 (ArH), 118.4 (C=C–S),
116.8 (ArH), 111.7 (ArH), 56.2 (OCH3), 45.6 (CH2), 39.4 (CH); HRMS
(ESI) m/z, [M + Na]+ calcd 333.0561; found: 333.0562; Anal. calcd
for C18H14O3S: C, 69.66; H, 4.55; S, 10.33; found: C, 69.76; H, 4.41; S,
10.43%.
(C=C–S), 116.9 (Ar–C), 50.8 (CH2), 41.0 (CH). HRMS (ESI) m/z, [M
+ Na]+ calcd 380.9561; found: 380.9554; Anal. calcd for C17H11BrO2S: C,
56.84; H, 3.09; S, 8.93; found: C, 56.61; H, 2.89; S, 9.04%.
2-(4-Bromophenyl)-1H-thieno[2,3-c]chromen-4(2H)-one (10e)
CAS No.: 145626-21-7; white solid, yield 52.8%; m.p. 181–182 °C; IR
(KBr), νmax cm–1: 3067 (Ar=C–H), 1713 (C=O), 1645 (C=C), 1542 (Ar);
1H NMR (DMSO-d6, 400 MHz): δ 7.64 (dd, J = 7.8, 1.4 Hz, 1H, ArH),
7.61–7.53 (m, 3H, ArH), 7.46–7.37 (m, 4H, ArH), 5.39 (dd, J = 9.5, 6.6
Hz, 1H, CH), 4.06 (dd, J = 18.1, 9.6 Hz, 1H, CH2), 3.76 (dd, J = 18.1, 6.9
Hz, 1H, CH2); 13C NMR (DMSO-d6, 100 MHz): δ 156.5 (C=O), 153.1
(Ar–C), 147.4 (C=C–S), 141.9 (Ar–C), 132.2 (Ar–C), 131.1 (Ar–C),
130.0 (Ar–C), 126.6 (Ar–C), 125.7 (Ar–C), 125.4 (Ar–C), 121.4 (Ar–C),
118.3 (C=C–S), 116.8 (Ar–C), 50.8 (CH2), 43.1 (CH); Anal. calcd for
C17H11BrO2S: C, 56.84; H, 3.09; S, 8.93; found: C, 56.43; H, 3.06, S,
9.17%.
2-(4-Methoxyphenyl)-1H-thieno[2,3-c]chromen-4(2H)-one (10m)
CAS No.: 73386-31-9; white solid, yield 44.3%; m.p. 136–137 °C; IR
(KBr), νmax cm–1: 3012 (Ar=C–H), 1718 (C=O), 1643 (C=C), 1541 (Ar),
1247 (Ar–O–CH3);1H NMR (DMSO-d6, 400 MHz): δ 7.65 (dd, J = 7.8,
1.2 Hz, 1H, ArH), 7.56 (dd, J = 7.2, 1.3 Hz, 1H, ArH), 7.47 (d, J = 8.3 Hz,
1H, ArH), 7.43–7.35 (m, 3H, ArH), 6.94–6.89 (m, 2H, ArH), 5.41 (t, J =
8.6 Hz, 1H, CH), 4.01 (dd, J = 18.0, 9.3 Hz, 1H, CH2), 3.76 (s, 3H, OCH3),
3.74 (dd, J = 18.4, 7.6 Hz, 1H, CH2);13C NMR (DMSO-d6, 100 MHz): δ
159.4 (C=O), 156.5 (ArH), 153.0 (ArH), 147.6 (C=C–S), 133.8 (ArH),
131.0 (ArH), 128.9 (ArH), 126.8 (ArH), 125.6 (ArH), 125.3 (ArH), 118.4
(C=C–S), 116.8 (ArH), 114.6 (ArH), 55.6 (OCH3), 51.6 (CH2), 43.3
(CH); Anal. calcd for C18H14O3S: C, 69.66; H, 4.55; S, 10.33; found: C,
69.42; H, 4.73; S, 10.45%.
2-(2-Fluorophenyl)-1H-thieno[2,3-c]chromen-4(2H)-one (10f)
White solid, yield 50.3%; m.p. 141–143 °C; IR (KBr), νmax cm–1: 3096
(Ar=C–H), 1715 (C=O), 1645 (C=C), 1547 (Ar); 1H NMR (DMSO-d6,
400 MHz): δ 7.69 (dd, J = 7.8, 1.1 Hz, 1H, ArH), 7.62–7.47 (m, 3H, ArH),
7.43–7.35 (m, 2H, ArH), 7.23 (dt, J = 10.1, 7.6 Hz, 2H, ArH), 5.55 (dd,
J = 9.7, 6.2 Hz, 1H, CH), 4.06 (dd, J = 18.1, 9.7 Hz, 1H, CH2), 3.86 (dd,
J = 18.1, 6.2 Hz, 1H, CH2); 13C NMR (DMSO-d6, 100 MHz): δ 160.1 (d,
JC–F = 244.5 Hz, Ar–C), 156.5 (C=O), 153.0 (Ar–C), 147.6 (C=C–S),
131.1 (Ar–C), 130.5 (d, JC–F = 8.4 Hz, Ar–C), 129.1 (d, JC–F = 13.2 Hz,
Ar–C), 129.0 (d, JC-F = 3.4 Hz, Ar–C), 126.3 (Ar–C), 125.7 (Ar–C), 125.4
(Ar–C), 118.3 (C=C–S), 116.9 (Ar–C), 116.2 (d, JC–F = 21.3 Hz, Ar–C),
44.6 (d, JC–F = 2.7 Hz, CH2), 41.6 (CH). HRMS (ESI) m/z, [M + Na]+
calcd 321.0361; found: 321.0360; Anal. calcd for C17H11FO2S: C, 68.44;
H, 3.72; S, 10.75; found: C, 68.17; H, 3.84; S, 10.78%.
Synthesis of substituted flavanones (8c–g, 8i–k, 8n); general procedure
These compounds were synthesised according to the literature
procedures.21 A suspension of compound 7 (10 mmol) in acetic acid
(25 mL) and a catalytic amount of methanesulphonic acid (10 mol %)
was refluxed for 2 h. The reaction solution was diluted with water (150
mL). The product was extracted with dichloromethane (20 mL × 3),
dried over anhydrous sodium sulfate, and the solvent was evaporated in
vacuo to give an oily liquid, which was the crude product. It was difficult
to separate the products because of their similar Rf value between
chalcones and products.
2-(3-Fluorophenyl)-1H-thieno[2,3-c]chromen-4(2H)-one (10g)
White solid, yield 48.7%; m.p. 146–148 °C; IR (KBr), νmax cm–1: 3094
(Ar=C–H), 1717 (C=O), 1641 (C=C), 1549 (Ar); 1H NMR (DMSO-d6,
400 MHz): δ 7.65 (dd, J = 7.8, 1.4 Hz, 1H, ArH), 7.61–7.5 (m, 1H,
ArH), 7.48 (dd, J = 8.3, 0.7 Hz, 1H, ArH), 7.44–7.31 (m, 4H, ArH),
7.18–7.12 (m, 1H, ArH), 5.42 (dd, J = 9.5, 7.2 Hz, 1H, CH), 4.07 (dd,
J = 18.1, 9.5 Hz, 1H, CH2), 3.80 (dd, J = 18.1, 7.2 Hz, 1H, CH2); 13C NMR
(DMSO-d6, 100 MHz): δ 162.7 (d, JC–F = 242.5 Hz, Ar–C), 156.5 (C=O),
153.1 (Ar–C), 147.5 (C=C–S), 145.2 (d, JC–F = 7.3 Hz, Ar–C), 131.3 (d,
Synthesis of 1H-thieno[2,3-c]chromen-4(2H)-one derivatives (10c–g,
10i–k, 10n); general procedure
The crude products 8 were directly reacted with thiazolidine-2,4-dione
(1.4 g, 12 mmol) in ethanol (30 mL) in the presence of piperidine at 78 °C
for 20 h. The white crude product was precipitated when the reaction
mixture was cooled to room temperature with stirring. Then, it was
filtered, washed with ethanol, dried, and recystallised from methanol to
obtain pure products 10 with about 40% yields.
JC–F = 8.4 Hz, Ar–C), 131.1 (Ar–C), 126.6 (Ar–C), 125.7 (Ar–C), 125.3
(Ar–C), 123.8 (d, JC–F = 2.7 Hz, Ar–C), 118.3 (C=C–S), 116.9 (Ar–C),
115.2 (d, JC–F = 20.9 Hz, Ar–C), 114.6 (d, Ar–C, JC–F = 21.9 Hz), 50.9
(CH2), 43.3 (CH). Anal. calcd for C17H11FO2S: C, 68.44; H, 3.72; S,
10.75; found: C, 68.23; H, 3.92; S, 10.41%.
2-(3,4-Dichlorophenyl)-1H-thieno[2,3-c]chromen-4(2H)-one (10c)
White solid, yield 42.7%; m.p. 206–208 °C; IR (KBr), νmax cm–1: 3015
(Ar=C–H), 1721 (C=O), 1639 (C=C), 1540 (Ar); 1H NMR (DMSO-d6,
400 MHz): δ 7.78 (d, J = 2.1 Hz, 1H, ArH), 7.65–7.56 (m, 3H, ArH), 7.48
(dd, J = 8.4, 2.2 Hz, 2H, ArH), 7.39 (td, J = 7.7, 1.1 Hz, 1H, ArH), 5.42
(dd, J = 9.7, 6.7 Hz, 1H, CH), 4.07 (dd, J = 18.2, 9.7 Hz, 1H, CH2), 3.81
(dd, J = 18.2, 6.7 Hz, 1H, CH2); 13C NMR (DMSO-d6, 100 MHz): δ 156.5
(C=O), 153.1 (Ar–C), 147.3 (C=C–S), 143.7 (Ar–C), 131.7 (Ar–C), 131.5
(Ar–C), 131.1 (Ar–C), 130.9 (Ar–C), 130.0 (Ar–C), 128.0 (Ar–C), 126.4
(Ar–C), 125.4 (Ar–C), 118.3 (C=C-S), 116.9 (Ar–C), 50.0 (CH2), 43.1
(CH); HRMS (ESI) m/z, [M + Na]+ calcd 370.9676; found: 370.9676;
Anal. calcd for C17H10Cl2O2S: C, 58.47; H, 2.89; S, 9.18; found: C, 58.83;
H, 3.12; S, 9.37%.
2-(o-Tolyl)-1H-thieno[2,3-c]chromen-4(2H)-one (10i)
CAS No.: 73386-26-2; white solid, yield 43.8%; m.p. 151–152 °C; IR
(KBr), νmax cm–1: 3071 (Ar=C–H), 1711 (C=O), 1646 (C=C), 1547 (Ar),
1376 (CH3); 1H NMR (DMSO-d6, 400 MHz): δ 7.70 (d, J = 7.6 Hz, 1H,
ArH), 7.59 (t, J = 7.8 Hz, 1H, ArH), 7.47 (dd, J = 11.8, 5.5 Hz, 2H, ArH),
7.40 (t, J = 7.5 Hz, 1H, ArH), 7.25–7.16 (m, 3H, ArH), 5.55 (dd, J = 9.1,
6.9 Hz, 1H, CH), 4.01 (dd, J = 18.0, 9.4 Hz, 1H, CH2), 3.81 (dd, J = 18.0,
6.7 Hz, 1H, CH2), 2.39 (s, 3H, CH3); 13C NMR (DMSO-d6, 100 MHz): δ
156.6 (C=O), 153.0 (Ar–C), 147.9 (C=C–S), 139.8 (Ar–C), 135.9 (Ar–
C), 131.0 (Ar–C), 130.9 (Ar–C), 128.2 (Ar–C), 127.0 (Ar–C), 126.6 (Ar–
C), 125.7 (Ar–C), 125.4 (Ar–C), 125.4 (Ar–C), 118.3 (C=C-S), 116.9
(Ar–C), 48.4 (CH2), 41.8 (CH), 19.7 (CH3); HRMS (ESI) m/z, [M + Na]+
calcd 317.0612; found: 317.0613; Anal. calcd for C18H14O2S: C, 73.44; H,
4.79; S, 10.89; found: C, 73.56; H, 4.62; S, 10.81%.
2-(2-Bromophenyl)-1H-thieno[2,3-c]chromen-4(2H)-one (10d)
CAS No.: 145626-19-3; white solid, yield 49.3%; m.p. 165–167 °C; IR
(KBr), νmax cm–1: 3062 (Ar =C–H), 1713 (C=O), 1645 (C=C), 1542
(Ar); 1H NMR (DMSO-d6, 400 MHz): δ 7.72 (m, 2H, ArH), 7.60 (m, 1H,
ArH), 7.50 (m, 2H, ArH), 7.44–7.35 (m, 2H, ArH), 7.26 (td, J = 7.7, 1.6
Hz, 1H, ArH), 5.52 (dd, J = 9.4, 5.0 Hz, 1H, CH), 4.05 (dd, J = 18.3, 9.4
Hz, 1H, CH2), 3.93 (dd, J = 18.2, 5.0 Hz, 1H, CH2); 13C NMR (DMSO-d6,
100 MHz): δ 156.6 (C=O), 153.1 (Ar–C), 147.7 (C=C–S), 141.0 (Ar–C),
133.4 (Ar–C), 131.2 (Ar–C), 130.3 (Ar–C), 129.0 (Ar–C), 128.3 (Ar–
C), 126.1 (Ar–C), 125.8 (Ar–C), 125.4 (Ar–C), 123.7 (Ar–C), 118.3
2-(m-Tolyl)-1H-thieno[2,3-c]chromen-4(2H)-one (10j)
CAS No.: 73386-27-3; white solid, yield 44.5%; m.p. 153–154 °C; IR
(KBr), νmax cm–1: 3057 (Ar=C–H), 1710 (C=O), 1640 (C=C), 1542 (Ar),
1373 (CH3);1H NMR (DMSO-d6, 400 MHz): δ 7.64 (dd, J = 7.8, 1.3 Hz,
1H, ArH), 7.58 (m, 1H, ArH), 7.47 (dd, J = 8.3, 0.8 Hz, 1H, ArH), 7.39
(td, J = 7.8, 1.1 Hz, 1H, ArH), 7.33–7.22 (m, 3H, ArH), 7.15–7.10 (m, 1H,
ArH), 5.37 (dd, J = 9.4, 8.1 Hz, 1H, CH), 4.04 (dd, J = 18.1, 9.5 Hz, 1H,
CH2), 3.75 (dd, J = 18.1, 8.0 Hz, 1H, CH2), 2.30 (s, 3H, CH3); 13C NMR