Yingjie Liu et al.
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765 cmÀ1; MS (ESI): m/z=256.0 [(M+1)]+; anal. calcd. for
C14H9NO2S: C 65.87, H 3.55, N 5.49; found: C 65.68, H 3.42,
N 5.46.
106.1, 108.2, 112.0, 113.0, 127.6, 149.6, 155.3, 163.0, 163.9; IR
(KBr): n=3357, 2998, 1659, 1232, 1058, 797 cmÀ1; MS (ESI):
m/z=267.0 [(M+1)]+; anal. calcd. for C13H14O4S: C 58.63,
H 5.30; found: C 58.49, H 5.18.
3i: Yellow solid; mp 228–2308C; 1H NMR (500 MHz,
DMSO): d=2.74 (s, 3H), 6.77 (s, 1H), 7.51 (t, J=7.5 Hz,
1H), 7.58 (t, J=7.5 Hz, 2H), 7.66 (t, J=7.5, 1H), 7.70 (t, J=
7.5, 1H), 7.76 (d, J=7.5 Hz, 2H), 8.19 (d, J=8.5 Hz, 2H),
10.15 (s, 1H); 13C NMR (125 MHz, DMSO): d=14.5, 99.8,
118.4, 119.7, 120.7, 122.9 (2C), 123.7, 125.1, 128.0, 129.0
(2C), 129.2 (2C), 133.1, 139.4, 144.7, 150.9, 160.6, 190.3; IR
(KBr): n=3185, 3035, 1602, 1589, 917, 761 cmÀ1; MS (ESI):
m/z=335.1 [(M+1)]+; anal. calcd. for C20H14O3S: C 71.84,
H 4.22; found: C 71.69, H 4.11.
3p: White solid; mp 174–1768C; 1H NMR (500 MHz,
DMSO): d=1.38 (t, J=7.0 Hz, 3H), 1.43 (t, J=7.0 Hz, 3H),
3.35 (q, J=7.5 Hz, 2H), 4.33 (q, J=7.5 Hz, 2H), 7.35 (s,
1H), 7.49 (t, J=7.5 Hz, 1H), 7.63 (t, J=7.0 Hz, 1H), 8.11
(d, J=8.0 Hz, 1H), 8.20 (d, J=8.0 Hz, 1H), 10.27 (s, 1H);
13C NMR (125 MHz, DMSO): d=14.9, 15.9, 25.6, 60.8,
100.2, 109.5, 119.5, 120.7, 122.8, 123.0, 123.9, 124.9, 128.0,
144.5, 151.3, 160.1, 163.6; IR (KBr): n=3278, 3005, 1663,
1376, 1129, 989 cmÀ1; MS (ESI): m/z=317.1 [(M+1)]+; anal.
calcd. for C17H16O4S: C 64.54, H 5.10; Found: C 64.68, H
5.19.
3j: Yellow solid; mp 242–2448C; 1H NMR (500 MHz,
DMSO): d=2.84 (s, 3H), 7.46 (s, 1H), 7.50–7.54 (m, 4H),
7.66–7.69 (m, 2H), 7.74 (d, J=15.5 Hz, 1H), 7.82 (d, J=
7.0 Hz, 2H), 8.18 (d, J=8.5 Hz, 1H), 8.22(d, J=8.5 Hz, 1H),
10.32 (s, 1H); 13C NMR (125 MHz, DMSO): d=14.1, 99.7,
119.0, 119.2, 120.2, 122.1, 122.3, 123.3, 124.6, 124.8, 127.5,
128.6 (2C), 129.2 (2C), 130.7, 134.6, 142.4, 144.3, 150.9,
160.2, 184.4; IR (KBr): n=3152, 2930, 1638, 1556, 1251,
765 cmÀ1; MS (ESI): m/z=361.1 [(M+1)]+; anal. calcd. for
C22H16O3S: C 73.31, H 4.47; found: C 73.10, H 4.39.
3k: White solid; mp 186–1888C; 1H NMR (500 MHz,
DMSO): d=1.33 (t, J=7.0 Hz, 3H), 2.65 (s, 3H), 4.32 (q,
J=7.0 Hz, 2H), 7.14 (s, 1H), 10.54 (s, 1H); 13C NMR
(125 MHz, DMSO): d=14.6, 14.7, 61.6, 98.6, 102.0, 112.6,
115.4, 127.5, 146.2, 152.8, 160.5, 162.5; IR (KBr): n=3242,
2985, 1637, 1370, 1169, 865 cmÀ1; MS (ESI): m/z=409.0
[(M+1)]+; anal. calcd. for C12H10Br2O4S: C 35.15, H 2.46;
found: C 35.33, H 2.37.
3q: White solid; mp 178–1808C; 1H NMR (500 MHz,
CDCl3): d=1.42–1.48 (m, 6H), 3.22 (q, J=7.0 Hz, 2H), 4.33
(q, J=7.0 Hz, 2H), 6.42 (s, broad, 1H), 7.17 (s, 1H);
13C NMR (125 MHz, CDCl3): d=14.3, 15.1, 26.3, 61.3, 98.9,
102.9, 111.7, 114.8, 126.7, 147.1, 150.7, 162.2, 162.6; IR
(KBr): n=3241, 2983, 2927, 1636, 1171, 867 cmÀ1; MS (ESI):
m/z=423.0 [(M+1)]+; anal. calcd. for C13H12Br2O4S: C
36.82, H 2.85; found: C 36.63, H 2.71.
3r: White solid; mp 182–1848C; 1H NMR (500 MHz,
DMSO): d=1.36 (t, J=7.0 Hz, 3H), 3.27 (q, J=7.0 Hz,
2H), 6.78 (s, 1H), 7.52 (t, J=8.0 Hz, 1H), 7.58 (t, J=7.5 Hz,
2H), 7.66–7.72 (m, 2H), 7.77 (d, J=7.5 Hz, 2H), 8.19 (d, J=
8.5 Hz, 2H), 10.17 (s, 1H); 13C NMR (125 MHz, DMSO):
d=15.8, 27.0, 99.8, 119.8, 120.0, 120.9, 123.0, 123.2, 123.9,
125.4, 128.2, 129.3 (2C), 129.4 (2C), 133.4, 139.3, 144.9,
151.1, 158.9, 190.6; IR (KBr): n=3202, 2967, 1594, 1429,
1148, 912 cmÀ1; MS (ESI): m/z=349.1 [(M+1)]+; anal.
calcd. for C21H16O3S: C 72.39, H 4.63; found: C 72.58, H
4.74.
3l: White solid; mp 214–2168C; 1H NMR (500 MHz,
DMSO): d=2.55 (s, 3H), 7.20 (s, 1H), 7.53 (t, J=7.5 Hz,
2H), 7.69 (t, J=7.0 Hz, 1H), 7.82 (d, J=7.0 Hz, 2H), 10.58
(s, 1H); 13C NMR (125 MHz, DMSO): d=15.9, 97.9, 101.7,
115.8, 121.5, 128.5, 129.0 (2C), 129.4 (2C), 134.1, 137.8,
145.9, 151.9, 154.4, 189.6; IR (KBr): n=3148, 2992, 1599,
1461, 1159, 887 cmÀ1; MS (ESI): m/z=440.9 [(M+1)]+; anal.
calcd. for C16H10Br2O3S: C 43.47, H 2.28; found: C 43.29, H
2.36.
General Procedure for the Synthesis of 4 (with 4a as
an Example)
To a solution of 3d (284 mg, 1.0 mmol) in 5.0 mL of ethanol,
was added butan-1-amine (0.03 mL, 3.0 mmol). The resulting
mixture was stirred under reflux. After completion of the re-
action as indicated by TLC, the reaction mixture was
poured into saturated aqueous NaCl (20 mL), neutralized
with dilute HCl, and extracted with CH2Cl2 (3ꢂ20 mL). The
combined organic phase was washed with water (3ꢂ20 mL),
dried over MgSO4 and concentrated under vacuum. The
crude product was purified by flash chromatography (silica
gel, petroleum ether:diethyl ether=5:1) to give 4a as yellow
crystals; yield: 271 mg (88%).
3m: White solid; mp 178–1808C; 1H NMR (500 MHz,
DMSO): d=1.32 (t, J=7.0 Hz, 3H), 2.34 (s, 6H), 2.63 (s,
3H), 4.28 (d, J=7.0 Hz, 2H), 6.62 (s, 1H), 9.08 (s, 1H);
13C NMR (125 MHz, DMSO): d=13.4, 13.8, 14.7 (2C), 60.9,
110.2, 113.0, 113.6, 117.9, 125.6, 148.3, 152.4, 161.1, 163.7; IR
(KBr): n=3355, 2985, 1638, 1369, 1152, 858 cmÀ1; MS (ESI):
m/z=281.1 [(M+1)]+; anal. calcd. for C14H16O4S: C 59.98,
H 5.75; found: C 59.76, H 5.63.
3n: White solid; mp 220–2228C; 1H NMR (500 MHz,
DMSO): d=1.74 (s, 3H), 2.40 (s, 3H), 2.52 (s, 3H), 6.70 (s,
1H), 7.54 (t, J=7.5 Hz, 2H), 7.68 (t, J=7.5 Hz, 1H), 7.78
(d, J=7.0 Hz, 2H), 9.12 (s, 1H); 13C NMR (125 MHz,
DMSO): d=13.2, 15.0, 16.1, 112.1, 114.7, 118.5, 121.6, 127.0,
129.5 (2C), 129.7 (2 C), 134.2, 138.6, 148.4, 152.0, 154.0,
Physical Data of Compounds Isolated
4a: Yellow crystals; mp 202–2048C; 1H NMR (500 MHz,
DMSO): d=0.92 (t, J=7.0 Hz, 3H), 1.32–1.38 (m, 2H),
1.60–1.65 (m, 2H), 3.51 (d, J=5.5 Hz, 2H), 6.07 (d, J=
2.5 Hz, 1H), 6.39 (dd, J=6.0, 8.5 Hz, 1H), 7.15 (d, J=
8.5 Hz, 1H), 7.51–7.58 (m, 5H), 9.02 (s, broad, 1H), 9.11 (s,
1H); 13C NMR (125 MHz, DMSO): d=14.1, 20.0, 32.2, 41.8,
93.2, 104.9, 108.9, 110.8, 127.4 (2C), 127.6, 129.0 (2C), 130.9,
141.8, 143.0, 154.5, 167.0, 188.5; IR (KBr): n=3196, 2958,
1657, 1531, 1366, 1171, 751 cmÀ1; MS (ESI): m/z=310.1
[(M+1)]+; anal. calcd. for C19H19NO3: C 73.77, H 6.19, N
4.53; found: C 73.59, H 6.27, N 4. 59.
191.8; IR (KBr): n=3284, 2969, 1592, 1460, 1190, 887 cmÀ1
;
MS (ESI): m/z=313.1 [(M+1)]+; anal. calcd. for C18H16O3S:
C 69.21, H 5.16; found: C 69.38, H 5.23.
3o: White solid; mp 154–1568C; 1H NMR (500 MHz,
DMSO): d=1.31–1.36 (m, 6H), 3.20 (q, J=7.0 Hz, 2H),
4.27 (q, J=7.5 Hz, 2H), 6.69 (dd, J=2.0, 9.0 Hz, 1H), 7.16
(d, J=2.0 Hz, 1H), 7.38 (d, J=9.0, 1H), 9.57 (s, 1H);
13C NMR (125 MHz, DMSO): d=15.1, 16.2, 25.5, 61.1,
890
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 884 – 892