E
A. B. Abdelwahab et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3): δ = 6.82 (s, 2 H), 2.92–2.87 (m, 2 H), 2.78–
HRMS (ESI): m/z calcd for [C14H21NOS + Na]+: 274.1207; found:
2.72 (m, 2 H), 2.44–2.38 (m, 2 H), 2.38 (s, 3 H).
274.1236.
13C NMR (100 MHz, CDCl3): δ = 193.7, 168.6, 141.0, 121.3, 112.2,
31.74, 29.1, 28.7, 27.3.
Anal. Calcd for C14H21NOS: C, 66.89; H, 8.42; N, 5.57; S, 12.76. Found:
C, 66.41; H, 8.42; N, 5.55; S, 13.03.
HRMS (ESI): m/z calcd for [C9H11NOS + Na]+: 204.0454; found:
204.0464.
1-(2-Amino-5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophen-3
yl)ethanone (4f)
Anal. Calcd for C9H11NOS: C, 59.64; H, 6.12; N, 7.73; S, 17.69. Found: C,
60.14; H, 6.10, N, 7.48; S, 17.25.
Yield: 1.7 g (32%); brown solid; mp 129–130 °C (toluene).
1H NMR (400 MHz, CDCl3): δ = 6.62 (s, 2 H), 2.87–2.79 (m, 2 H), 2.61–
2.59 (m, 2 H), 2.43 (s, 1 H), 1.89–1.83 (m, 2 H), 1.75–1.64 (m, 4 H).
1-(2-Amino-4,5,6,7-tetrahydrobenzo[b]thiophen-3-yl)ethanone
13C NMR (100 MHz, CDCl3): δ = 194.6, 161.4, 136.1, 121.1, 118.5, 31.7,
(4b)
Yield: 2.8 g (58%); brown solid; mp 114–117 °C (toluene).
31.0, 29.8, 28.4, 27.6, 26.6.
1H NMR (400 MHz, CDCl3): δ = 6.94 (s, 2 H), 2.74–2.67 (m, 2 H), 2.58–
HRMS (ESI): m/z calcd for [C11H15NOS + Na]+: 232.0767; found:
2.52 (m, 2 H), 2.42 (s, 3 H), 1.86–1.79 (m, 4 H).
232.0778.
13C NMR (100 MHz, CDCl3): δ = 194.1, 163.9, 130.6, 117.6, 115.8, 30.7,
28.1, 24.7, 23.1, 22.9.
Anal. Calcd for C11H15NOS: C, 63.12; H, 7.22; N, 6.69; O, 7.64; S, 15.32.
Found: C, 62.99; H, 7.13; N, 7.11; S, 15.08.
HRMS (ESI): m/z calcd for [C10H13NOS + Na]+: 218.0610; found:
218.0602.
1-(2-Amino-4,5-dimethylthiophen-3-yl)ethanone (4g)
Yield: 1.5 g (36%); brown solid; mp 154–157 °C.
1H NMR (400 MHz, CDCl3): δ = 6.87 (s, 2 H), 2.46 (s, 3 H), 2.23 (s, 3 H),
Anal. Calcd for C10H13NOS: C, 61.50; H, 6.71; N, 7.17; O, 8.19; S, 16.42.
Found: C, 61.85; H, 6.65, N, 6.86; S, 16.18.
2.18 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 194.4, 163.1, 128.4, 117.0, 113.8, 30.6,
15.8, 12.6.
1-(2-Amino-5-methyl-4,5,6,7-tetrahydrobenzo[b]thiophen-3-
yl)ethanone (4c)
Yield: 1.5 g (28%); greenish solid; mp 180–182 °C (abs. EtOH).
HRMS (ESI): m/z calcd for [C8H11NOS
+
H]+: 170.634; found:
1H NMR (400 MHz, CDCl3): δ = 6.97 (s, 2 H), 2.83 (dd, J = 15.6, 4.5 Hz,
1 H), 2.60–2.53 (m, 2 H), 2.42 (s, 3 H), 2.30–2.15 (m, 1 H), 2.01–1.76
(m, 2 H), 1.51–1.36 (m, 1 H), 1.10 (d, J = 6.6 Hz, 3 H).
170.0633; calcd for [C8H11NOS + Na]+: 192.0454; found: 192.0456.
Anal. Calcd for C8H11NOS: C, 56.77; H, 6.55; N, 8.28; S, 18.95. Found: C,
56.65; H, 6.41; N, 9.07; S, 19.07.
13C NMR (100 MHz, CDCl3): δ = 194.0, 164.3, 130.6, 117.3, 115.7, 36.6,
31.0, 30.6, 29.3, 24.5, 22.1.
HRMS (ESI): m/z calcd for [C11H15NOS – H + Na]+: 231.0694; found:
1-(2-Amino-4-methyl-5-propylthiophen-3-yl)ethanone (4h)
Yield: 4.9 g (30%); brown solid; mp 113–115 °C (cyclohexane).
231.0699.
1H NMR (400 MHz, CDCl3): δ = 2.56 (t, J = 7.6 MHz, 2 H), 2.47 (s, 3 H),
2.24 (s, 3 H), 1.57 (m, 2 H), 0.96 (t, J = 7.2, 3 H).
13C NMR (100 MHz, CDCl3): δ = 194.4, 163.3, 128.0, 120.0, 13.6, 117.0,
Anal. Calcd for C11H15NOS: C, 63.12; H, 7.22; N, 6.69; S, 15.32. Found:
C, 62.84; H, 7.12; N, 6.53; S, 15.12.
30.6, 29.2, 24.4, 15.86.
HRMS (ESI): m/z calcd for [C10H15NOS + Na]+: 220.0767; found:
220.0781.
1-(2-Amino-6-methyl-4,5,6,7-tetrahydrobenzo[b]thiophen-3
yl)ethanone (4d)
Yield: 1.5 g (28%); greenish solid; mp 127 °C (cyclohexane).
Anal. Calcd for C10H15NOS: C, 60.88; H, 7.66; N, 7.10; S, 16.25. Found:
C, 60.55; H, 7.58; N, 7.20; S, 16.70.
1H NMR (400 MHz, CDCl3): δ = 6.79 (s, 2 H), 2.85–2.76 (m, 1 H), 2.72–
2.61 (m, 1 H), 2.61–2.54 (m, 1 H), 2.41 (s, 3 H), 2.21–2.12 (m, 1 H),
1.95–1.86 (m, 2 H), 1.47–1.35 (m, 1 H), 1.07 (d, J = 6.5 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 194.0, 164.2, 130.2, 117.2, 115.6, 32.9,
31.3, 30.6, 29.2, 27.8, 21.4.
1-(2-Amino-4-methyl-5-pentylthiophen-3-yl)ethanone (4i)
Yield: 0.45 g (8%); greenish solid; mp 112–113 °C (cyclohexane).
1H NMR (400 MHz, CDCl3): δ = 2.59–2.53 (m, 2 H), 2.46 (s, 3 H), 2.24
(s, 3 H), 1.58–1.51 (m, 2 H), 1.39–1.28 (m, 4 H), 0.92 (t, J = 6.9 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 194.4, 163.4, 127.9, 120.3, 117.04,
31.3, 30.9, 27.3, 22.5, 15.8, 14.02.
HRMS (ESI): m/z calcd for [C9H16OS – H + Na]+: 232.0767; found:
232.0801.
Anal. Calcd for C11H15NOS: C, 63.12; H, 7.22; N, 6.69; S, 15.32. Found:
C, 62.61; H, 7.19; N, 6.88; S, 15.75.
HRMS (ESI): m/z calcd for [C12H19NOS – H + Na]+: 247.0993; found:
247.1001.
1-{2-Amino-6-(tert-butyl)-4,5,6,7-tetrahydrobenzo[b]thiophen-3-
Anal. Calcd for C12H19NOS: C, 63.96; H, 8.50; N, 6.22; S, 14.23. Found:
C, 64.01; H, 8.34; N, 6.17; S, 14.35.
yl}ethanone (4e)
Yield: 5.4 g (86%); beige-brown solid; mp 155–158 °C (cyclohexane).
1H NMR (400 MHz, CDCl3): δ = 6.99 (s, 1 H), 2.88 (ddt, J = 15.9, 4.7,
1.8 Hz, 1 H), 2.66–2.49 (m, 2 H), 2.40 (s, 3 H), 2.37–2.28 (m, 1 H),
2.07–2.00 (m, 1 H), 1.56–1.46 (m, 1 H), 1.40–1.28 (m, 1 H), 0.94 (s,
9 H).
13C NMR (100 MHz, CDCl3): δ = 194.0, 164.2, 130.6, 118.3, 115.5, 32.4,
30.5, 29.2, 27.2, 26.3, 24.7
1-(2-Amino-5,7-dihydro-4H-thieno[2,3-c]thiopyran-3-yl)etha-
none (4j)
Yield: 3.8 g (72%); brownish solid; mp 167–170 °C.
1H NMR (400 MHz, CDCl3): δ = 6.96 (s, 2 H), 3.62 (t, J = 1.6 Hz, 2 H),
3.02 (ddd, J = 5.8, 4.6, 1.2 Hz, 2 H), 2.93 (t, J = 5.5 Hz, 2 H), 2.42 (s, 3 H).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H