40
J. Debray et al.
LETTER
13
C NMR (75 MHz, CDCl ): δ = 191.9 (C ), 142.9 (C ),
192.7 (C ), 149.9 (C ), 142.4 (C ), 130.7 (C ), 128.9 (CH),
3
q
q
q
q
q
q
1
1
42.1 (C ), 137.0 (C ), 132.1 (C ), 130.6 (CH), 129.0 (CH),
126.8 (C ), 125.9 (CH), 122.4 (CH), 107.9 (C ), 29.3 (CH ).
q
q
q
q
q
3
+
28.7 (C ), 127.4 (CH), 127.2 (CH), 126.4 (CH), 124.2
ESI-MS (MeCN): m/z calcd: 225 [M + H] ; found: 226. ESI-
q
+
(CH), 122.8 (CH), 26.8 (CH ). ESI-MS (MeCN): m/z calcd:
HMRS: m/z [M + H] calcd for C H ClNOS: 226.0088;
3
10
9
+
+
226 [M + H] ; found: 227. ESI-HMRS: m/z [M + Na] calcd
found: 226.0093.
2-Acetyl-3-amino-7-methylbenzo[b]thiophene (2c)
for C H NaOS: 249.0345; found: 249.0349.
14
10
1
2-Acetyl-5,6-methylenedioxybenzo[b]thiophene (1e)
Brown solid; mp 110–111 °C (from Et O); yield 90%. H
2
1
Brown solid; mp 170–172 °C (from Et O); yield 35%. H
NMR (300 MHz, CDCl ): δ = 7.54–7.51 (1 H, m, Harom),
2
3
NMR (300 MHz, CDCl ): δ = 7.78 (1 H, s, H ), 7.25 (1 H,
7.35–7.31 (2 H, m, H ), 2.50 (3 H, s, CH ), 2.49 (3 H, s,
3
arom
arom
3
1
3
13
m, Harom), 6.06 (2 H, s, CH ), 2.60 (3 H, s, CH ). C NMR
CH3). C NMR (75 MHz, CDCl ): δ = 193.3 (C ), 149.6
2
3
3
q
(
75 MHz, CDCl ): δ = 191.7 (C ), 149.5 (C ), 147.6 (C ),
(C ), 140.2 (C ), 133.0 (C ), 131.2 (C ), 129.2 (CH), 124.7
q q q q
3
q
q
q
1
1
42.5 (C ), 138.2 (C ), 133.8 (C ), 129.5 (CH), 103.6 (CH),
(CH), 119.4 (CH), 108.9 (C ), 29.1 (CH ), 19.8 (CH ). ESI-
q
q
q
q 3 3
+
01.9 (CH ), 101.8 (CH), 26.8 (CH ). ESI-MS (MeCN): m/z
MS (MeCN): m/z calcd: 205 [M + H] ; found: 206. ESI-
2
3
+
+
+
calcd: 220 [M + H] ; found: 221. ESI-HMRS: m/z [M + Na]
HMRS: m/z [M + Na] calcd for C H NNaOS: 228.0454;
1
1
11
calcd for C H NaO S: 243.0086; found: 234.0079.
found: 228.0451.
2-Acetyl-3-amino-5-methoxybenzo[b]thiophene (2d)
1
1
8
3
2-Acetylpyrido[2,3-b]thiophene (1f)
1
1
White solid; mp 120–122 °C (from Et O); yield 86%. H
Brown solid; mp 116–117 °C (from Et O); yield 15%. H
2
2
NMR (300 MHz, CDCl ): δ = 8.67 (1 H, dd, J = 1.5, 4.5 Hz,
NMR (300 MHz, CDCl ): δ = 7.59 (1 H, d, J = 8.8 Hz, Harom),
3
3
Harom), 8.17 (1 H, dd, J = 1.5, 8.1 Hz, Harom), 7.87 (1 H, s,
Harom), 7.36 (1 H, dd, J = 4.5, 8.1 Hz, Harom), 2.66 (3 H, s,
7.16 (1 H, dd, J = 2.2, 8.8 Hz, Harom), 7.06 (1 H, d, J = 2.2
13
Hz, Harom), 3.89 (3 H, s, CH ), 2.45 (3 H, s, CH ). C NMR
3
3
1
3
CH3). C NMR (75 MHz, CDCl ): δ = 192.2 (C ), 163.5
(75 MHz, CDCl ): δ = 193.4 (C ), 157.6 (C ), 148.4 (C ),
3
q
3 q q q
(
C ), 149.7 (CH), 143.8 (C ), 133.7 (CH), 132.9 (C ), 127.0
132.4 (C ), 132.1 (C ), 124.5 (CH), 119.8 (CH), 110.4 (C ),
q q q
q
q
q
(
1
CH), 120.4 (CH), 26.8 (CH ). ESI-MS (MeCN): m/z calcd:
77 [M + H] ; found: 178. ESI-HMRS: m/z [M + Na] calcd
103.5 (CH), 55.8 (CH ), 29.0 (CH ). ESI-MS (MeCN): m/z
calcd: 221 [M + H] ; found: 222. ESI-HMRS: m/z [M + H]
3
3 3
+
+
+
+
for C H NaNOS: 200.0141; found: 200.0138.
calcd for C H NO S: 222.0593; found: 22.0589.
9
7
11 12
2
(
20) (a) Gschwend, H. W.; Rodriguez, H. R. Org. React. 1979,
6, 1. (b) Kudo, H.; Castle, R. N.; Lee, M. L. J. Heterocycl.
2-Acetyl-3-amino-5-nitrobenzo[b]thiophene (2e)
Orange solid; mp 290–292 °C (from MeOH); yield 99%. H
1
2
Chem. 1985, 22, 215. (c) Okuyama, T.; Tani, Y.; Miyake,
K.; Yokoyama, Y. J. Org. Chem. 2007, 72, 1634.
NMR (300 MHz, DMSO-d ): δ = 9.23 (1 H, d, J = 2.0 Hz,
6
Harom), 8.28 (1 H, dd, J = 2.0, 8.8 Hz, Harom), 8.09 (1 H, d, J
13
(
21) 2-Acetyl-3-aminobenzo[b]thiophene (2a)
= 8.8 Hz, Harom), 2.37 (3 H, s, CH3). C NMR (75 MHz,
1
Yellow solid; mp 146–148 °C (from Et O); yield 91%. H
DMSO-d ): δ = 191.7 (C ), 150.0 (C ), 145.0 (C ), 144.9
2
6
q
q
q
NMR (300 MHz, CDCl ): δ = 7.72 (1 H, d, J = 8.1 Hz, Harom),
(C ), 131.7 (C ), 124.9 (CH), 122.9 (CH), 120.2 (CH), 107.8
3
q q
+
7.67 (1 H, d, J = 8.1 Hz, Harom), 7.49 (1 H, dd, J = 7.5 Hz,
(C ), 29.2 (CH ). ESI-MS (MeCN): m/z calcd: 236 [M + H] ;
q 3
+
Harom), 7.36 (1 H, dd, J = 7.5 Hz, Harom), 6.52 (2 H, br s, NH2),
found: 237. HMRS (CI): m/z [M + H] calcd for
1
3
2
.46 (3 H, s, CH3). C NMR (75 MHz, CDCl ): δ = 193.3
C H N O S: 237.0328; found: 237.0327.
3
10
9
2
3
(
(
C ), 148.8 (C ), 139.9 (C ), 131.3 (C ), 129.0 (CH), 124.2
2-Acetyl-3-aminopyrido[2,3-b]thiophene (2f)
q
q
q
q
1
CH), 123.6 (CH), 121.9 (CH), 108.8 (C ), 29.2 (CH ). ESI-
Yellow solid; mp 194–196 °C (from Et O); yield 96%. H
q
3
2
+
MS (MeCN): m/z calcd: 191 [M + H] ; found: 192. ESI-
HMRS: m/z [M + H] calcd for C H NOS: 192.0478;
NMR (300 MHz, CDCl ): δ = 8.72 (1 H, dd, J = 1.5, 4.7 Hz,
3
+
Harom), 7.98 (1 H, dd, J = 1.5, 8.0 Hz, Harom), 7.33 (1 H, dd, J
1
0
10
found: 192.0470.
-Acetyl-3-amino-4-chlorobenzo[b]thiophene (2b)
= 4.7, 8.0 Hz, H ), 6.68 (2 H, br s, NH ), 2.49 (3 H, s,
arom
2
1
3
2
CH3). C NMR (75 MHz, CDCl ): δ = 193.9 (C ), 160.8
3
q
1
Yellow solid; mp 101–103 °C (from Et O); yield 82%. H
(C ), 151.3 (CH), 146.3 (C ), 130.0 (CH), 125.5 (C ), 119.2
q q q
2
NMR (300 MHz, CDCl ): δ = 7.59 (1 H, d, J = 8.0 Hz, Harom),
(CH), 108.0 (C ), 29.4 (CH ). ESI-MS(MeCN): m/z calcd:
192 [M + H] ; found: 193. ESI-HMRS: m/z [M + H] calcd
3
q 3
+
+
7
.34 (1 H, dd, J = 7.8 Hz, Harom), 7.27 (1 H, d, J = 7.5 Hz,
1
3
Harom), 2.43 (3 H, s, CH3). C NMR (75 MHz, CDCl ): δ =
for C H N OS: 193.0430; found: 193.0432.
3
9
9
2
Synlett 2013, 24, 37–40
© Georg Thieme Verlag Stuttgart · New York