10.1002/ejoc.201801686
European Journal of Organic Chemistry
FULL PAPER
(Z)-14-(4-(trifluoromethyl)benzylidene)-13,14-dihydro-6H-
Method A, starting from 3l (84 mg, 0.18 mmol), 4l was obtained after
purification by flash chromatography (5-40% AcOEt in cyclohexane) as a
beige solid (34 mg, 49%). TLC (heptane/AcOEt 1:1, Rf = 0.24). 1H NMR
(400 MHz, CDCl3) δ 3.75 (s, 3H), 4.49 (s, 2H), 5.54 (s, 2H), 6.41 (d, J =
2.3 Hz, 1H), 6.73 (dd, J = 2.4, 8.8 Hz, 1H), 6.90 (s, 1H), 7.11-7.13 (m, 2H),
7.20-7.22 (m, 1H), 7.28-7.40 (m, 7H), 7.48-7.50 (m, 1H). 13C NMR (100
MHz, CDCl3) δ 32.2, 45.4, 55.9, 93.0, 110.8, 119.7, 127.9, 128.6, 128.7,
128.8, 129.2, 130.2, 130.5, 133.5, 135.9, 136.0, 136.1, 136.3, 138.8, 144.4,
149.5, 156.5. HRMS (ESI-Q-TOF) m/z calcd for C24H20N2OS [M+H]+:
385.1374, found: 385.1353.
benzo[g]benzo[4,5]imidazo [2,1-c][1,4]thiazocine (4f): Following the
GP Method A, starting from 3f (90 mg, 0.18 mmol), 4f was obtained after
purification by flash chromatography (5-40% AcOEt in cyclohexane) as a
yellowish amorphous solid (28 mg, 37%). TLC (heptane/AcOEt 1:1, Rf =
0.36). 1H NMR (400 MHz, CDCl3) δ 4.53 (s, 2H), 5.57 (s, 2H), 6.86-6.93
(m, 2H), 7.05-7.21 (m, 5H), 7.38-7.45 (m, 2H), 7.46-7.55 (m, 2H), 7.60 (d,
J = 7.9 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 32.2, 45.0, 108.3, 119.36,
122.2, 122.6, 125.2, 125.5, 125.6, 125.6, 125.6, 128.8, 128.9, 129.2, 129.6,
130.4, 131.9, 135.1, 135.8, 139.4, 141.0, 141.7, 143.8, 150.1. HRMS (ESI-
Q-TOF) m/z calcd for C24H17F3N2S [M+H]+: 423.1143, found: 423.1124.
(Z)-14-benzylidene-9-methoxy-13,14-dihydro-6H-
(Z)-14-(3-fluorobenzylidene)-13,14-dihydro-6H-
benzo[g]benzo[4,5]imidazo[2,1-c][1,4]thiazocine (4m): Following the
GP Method A, starting from 3m (85 mg, 0.18 mmol), 4m was obtained after
purification by flash chromatography (5-40% AcOEt in cyclohexane as a
yellowish amorphous solid (27 mg, 38%). TLC (heptane/AcOEt 1:1, Rf =
0.18). 1H NMR (400 MHz, CDCl3) δ 3.75 (s, 3H), 4.49 (s, 2H), 5.58 (s, 2H),
6.73 (dd, J = 2.4, 8.8 Hz, 1H), 6.83-6.86 (m, 2H), 6.97 (d, J = 2.4 Hz, 1H),
7.09-7.13 (m, 2H), 7.16-7.18 (m, 1H), 7.29-7.42 (m, 5H), 7.47-7.49 (m, 1H).
13C NMR (100 MHz, CDCl3) δ 32.2, 45.7, 55.7, 101.6, 109.0, 112.5, 127.9,
128.6, 128.7, 128.9, 129.3, 129.9, 130.1, 130.2, 133.2, 136.0, 136.1, 138.9,
142.6, 144.6, 150.4, 156.1. HRMS (ESI-Q-TOF) m/z calcd for C24H20N2OS
[M+H]+: 385.1374, found: 385.1362.
benzo[g]benzo[4,5]imidazo[2,1-c] [1,4]thiazocine (4g): Following the
GP Method A, starting from 3g (79 mg, 0.18 mmol), 4g was obtained after
purification by flash chromatography (5-30% AcOEt in cyclohexane) as a
yellowish amorphous solid (26 mg, 40%). TLC (heptane/AcOEt 1:1, Rf =
0.49). 1H NMR (400 MHz, CDCl3) δ 4.54 (s, 2H), 5.62 (s, 2H), 6.83 (s, 1H),
6.96-7.03 (m, 2H), 7.06-7.17 (m, 7H), 7.34 (td, J = 6.0, 8.0 Hz, 1H), 7.48-
7.51 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 32.3, 45.4, 108.6, 114.8, 115.0,
115.6, 115.8, 119.4, 122.3, 122.7, 124.5, 124.6, 128.9, 129.4, 130.1, 130.2,
130.3, 130.4, 132.0, 132.0, 135.2, 136.2, 138.1, 138.2, 140.2, 144.3, 150.2,
161.7, 164.2. HRMS (ESI-Q-TOF) m/z calcd for C23H17FN2S [M+H]+:
373.1174, found: 373.1150.
(Z)-10-chloro-14-propylidene-13,14-dihydro-6H-
(Z)-14-(thiophen-3-ylmethylene)-13,14-dihydro-6H-
benzo[g]benzo[4,5]imidazo[2,1-c] [1,4]thiazocine (4n): Following the
GP Method A, starting from 3n (100 mg, 0.24 mmol), 4n was obtained after
purification by flash chromatography (0-3% Et2O in DCM) as a yellowish
amorphous solid (42 mg, 52%). TLC (heptane/AcOEt 4:1, Rf = 0.17). 1H
NMR (400 MHz, CDCl3) δ 0.85 (t, J = 7.5 Hz, 3H), 2.01 (quint, J = 7.5 Hz,
2H), 4.43 (s, 2H), 5.19 (s, 2H), 5.96 (t, J = 7.4 Hz, 1H), 7.15-7.25 (m, 4H),
7.37 (d, J = 1.9 Hz, 1H), 7.42-7.44 (m, 1H), 7.56 (d, J = 8.6 Hz, 1H). 13C
NMR (100 MHz, CDCl3) δ 13.1, 22.0, 31.4, 43.1, 108.9, 120.6, 122.9,
128.1, 128.2, 128.7, 131.0, 132.1, 132.8, 134.2, 136.2, 139.4, 140.4, 142.1,
152.1. HRMS (ESI-Q-TOF) m/z calcd for C19H17ClN2S [M+H]+: 341.0889,
found: 341.0865.
benzo[g]benzo[4,5]imidazo[2,1-c] [1,4]thiazocine (4h): Following the
GP Method A, starting from 3h (79 mg, 0.18 mmol), 4h was obtained after
purification by flash chromatography (5-40% AcOEt in cyclohexane) as a
yellowish amorphous solid (24 mg, 37%). TLC (heptane/AcOEt 1:1, Rf =
0.33). 1H NMR (400 MHz, CDCl3) δ 4.55 (s, 2H), 5.63 (s, 2H), 6.82 (s, 1H),
7.09-7.17 (m, 5H), 7.25-7.26 (m, 2H), 7.36 (dd, J = 2.9, 5.0 Hz, 1H), 7.47-
7.49 (m, 1H), 7.52-7.55 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 32.0, 45.9,
108.8, 119.4, 122.4, 122.8, 124.6, 126.2, 127.4, 128.6, 128.6, 129.2, 130.2,
130.5, 135.3, 135.7, 137.0, 137.4, 141.7, 144.7, 150.5. HRMS (ESI-Q-
TOF) m/z calcd for C21H16N2S2 [M+H]+: 361.0833, found: 361.0820.
14-methylene-13,14-dihydro-6H-benzo[g]benzo[4,5]imidazo[2,1-
c][1,4]thiazocine (4i): Following the GP Method A, starting from 3i (100
mg, 0.28 mmol), an inseparable mixture of 4i and 2a in a ratio 2:1 was
obtained (23 mg) after purification by flash chromatography (5-40% AcOEt
in pentane). 4i was characterized from the mixture. TLC (heptane/AcOEt
2:3, Rf = 0.49). 1H NMR (400 MHz, CDCl3) δ 4.53 (s, 2H), 5.47 (s, 2H),
5.51 (s, 1H), 5.54 (s, 1H), 7.13-7.28 (m, 5H), 7.34 (d, J = 8.0 Hz, 1H), 7.47-
7.51 (m, 1H), 7.59-7.62 (m, 1H). HRMS (ESI-Q-TOF) m/z calcd for
C17H14N2S [M+H]+: 279.0956, found: 279.0945.
(Z)-9-chloro-14-propylidene-13,14-dihydro-6H-
benzo[g]benzo[4,5]imidazo[2,1-c][1,4] thiazocine (4o): Following the
GP Method A, starting from 3o (100 mg, 0.24 mmol), 4o was obtained after
purification by flash chromatography (0-3% Et2O in DCM) as a yellowish
amorphous solid (26 mg, 32%). TLC (heptane/AcOEt 4:1, Rf = 0.22). 1H
NMR (400 MHz, CDCl3) δ 0.81 (t, J = 7.5 Hz, 3H), 1.97 (p, J = 7.5 Hz, 2H),
4.41 (s, 2H), 5.20 (s, 2H), 5.93 (t, J = 7.5 Hz, 1H), 7.13-7.22 (m, 3H), 7.23-
7.24 (m, 1H), 7.27 (d, J = 8.5 Hz, 1H), 7.40-7.42 (m, 1H), 7.61 (d, J = 1.8
Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 13.1, 21.9, 31.4, 43.1, 109.3, 119.6,
123.2, 127.7, 128.1, 128.2, 130.9, 132.1, 132.8, 134.32, 134.3, 139.2,
142.2, 142.6, 152.5. HRMS (ESI-Q-TOF) m/z calcd for C19H17ClN2S
[M+H]+: 341.0879, found: 341.0872.
(Z)-10-methoxy-14-propylidene-13,14-dihydro-6H-
benzo[g]benzo[4,5]imidazo[2,1-c] [1,4]thiazocine (4j): Following the
GP Method A, starting from 3j (100 mg, 0.24 mmol), 4j was obtained after
purification by flash chromatography (5-30% AcOEt in cyclohexane as an
orange oil (45 mg, 55%). TLC (heptane/AcOEt 1:1, Rf = 0.34). 1H NMR
(400 MHz, CDCl3) δ 0.83 (t, J = 7.5 Hz, 3H), 2.00 (quint, J = 7.5 Hz, 2H),
3.89 (s, 3H), 4.43 (s, 2H), 5.17 (s, 2H), 5.96 (t, J = 7.4 Hz, 1H), 6.85-6.89
(Z)-9,10-dimethyl-14-propylidene-13,14-dihydro-6H-
benzo[g]benzo[4,5]imidazo[2,1-c][1,4]thiazocine (4p): Following the
GP Method A, starting from 3p (100 mg, 0.24 mmol), 4p was obtained after
purification by flash chromatography (0-7% Et2O in DCM) as a yellowish
oil (34 mg, 42%). TLC (heptane/AcOEt 1:1, Rf = 0.43). 1H NMR (400 MHz,
CDCl3) δ 0.83 (t, J = 7.5 Hz, 3H), 2.00 (quint, J = 7.5 Hz, 2H), 2.35 (s, 3H),
2.41 (s, 3H), 4.43 (s, 2H), 5.16 (s, 2H), 5.94 (t, J = 7.4 Hz, 1H), 7.14-7.26
(m, 4H), 7.40-7.43 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 13.1, 20.3, 20.8,
21.9, 31.3, 42.8, 108.9, 119.7, 127.9, 127.9, 131.0, 131.1, 131.9, 132.4,
132.6, 134.2, 134.6, 139.2, 140.1, 142.1, 150.2. HRMS (ESI-Q-TOF) m/z
calcd for C21H22N2S [M+H]+: 335.1582, found: 335.1576.
(m, 2H), 7.16-7.25 (m, 3H), 7.41-7.43 (m, 1H), 7.55 (d, J = 8.7 Hz, 1H). 13
C
NMR (100 MHz, CDCl3) δ 13.1, 22.0, 31.4, 42.8, 56.0, 93.0, 110.9, 120.1,
128.0, 131.0, 132.5, 132.6, 134.4, 135.9, 136.2, 139.3, 142.1, 150.3, 156.8.
HRMS (ESI-Q-TOF) m/z calcd for C20H20N2OS [M+H]+: 337.1374, found:
337.1360.
(Z)-9-methoxy-14-propylidene-13,14-dihydro-6H-
benzo[g]benzo[4,5]imidazo[2,1-c] [1,4]thiazocine (4k): Following the
GP Method A, starting from 3k (87 mg, 0.21 mmol), 4k was obtained after
purification by flash chromatography (5-30% AcOEt in cyclohexane) as an
orange oil (37 mg, 53%). TLC (heptane/AcOEt 1:1, Rf = 0.29). 1H NMR
(400 MHz, CDCl3) δ 0.83 (t, J = 7.5 Hz, 3H), 2.01 (quint, J = 7.5 Hz, 2H),
3.84 (s, 3H), 4.44 (s, 2H), 5.20 (s, 2H), 5.94 (t, J = 7.4 Hz, 1H), 6.94 (dd, J
= 2.4, 8.8 Hz, 1H), 7.14-7.23 (m, 4H), 7.26 (d, J = 8.8 Hz, 1H), 7.41-7.43
(m, 1H). 13C NMR (100 MHz, CDCl3) δ 13.1, 21.9, 31.3, 43.0, 55.9, 101.9,
109.0, 112.8, 128.0, 128.1, 130.2, 130.9, 132.3, 132.7, 134.5, 139.1, 142.1,
142.2, 151.1, 156.2. HRMS (ESI-Q-TOF) m/z calcd for C20H20N2OS
[M+H]+: 337.1374, found: 337.1360.
(Z)-13-propylidene-13,14-dihydro-6H,8H-
benzo[g]benzo[4,5]imidazo[2,1-c][1,4] thiazonine (8a): Following the
GP Method A, starting from 7a (100 mg, 0.25 mmol), 8a was obtained after
purification by flash chromatography (5-30% AcOEt in heptane) as a
yellowish amorphous solid (37 mg, 46%). TLC (heptane/AcOEt 1:1, Rf =
0.24). 1H NMR (400 MHz, CDCl3) δ 1.18 (t, J = 7.5 Hz, 3H), 2.40 (p, J =
7.5 Hz, 2H), 3.81 (s, 2H), 4.00 (s, 2H), 5.16 (s, 2H), 5.65 (tt, J = 1.9, 7.3
Hz, 1H), 6.72-6.79 (m, 2H), 6.98 (td, J = 1.8, 7.3 Hz, 1H), 7.11-7.20 (m,
3H), 7.23 (d, J = 7.7 Hz, 1H), 7.50 (dt, J = 1.0, 7.8 Hz, 1H). 13C NMR (100
MHz, CDCl3) δ 13.9, 21.8, 27.6, 34.1, 44.5, 109.6, 119.5, 122.2, 122.4,
126.1, 128.3, 129.3, 129.8, 134.8, 135.6, 137.6, 138.1, 142.6, 152.6.
HRMS (ESI-Q-TOF) m/z calcd for C20H20N2S [M+H]+: 321.1425, found:
321.1435.
(Z)-14-benzylidene-10-methoxy-13,14-dihydro-6H-
benzo[g]benzo[4,5]imidazo[2,1-c][1,4]thiazocine (4l): Following the GP
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