108 Sakirolla et al.
Asian J. Chem.
2-(4-Phenyl-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-
C: 70.56; H: 5.41; N: 3.58; O: 12.26; S: 8.19. Found: C: 70.42;
H: 5.22; N: 3.44.
yl)phenol: Light yellow solid; m.p.: 112-115 ºC; 1H NMR (400
MHz, CDCl3): δ 15.28 (s, OH), 7.42-7.43 (m, 2H), 7.27-7.37
(m, 6H), 7.12 (td, J = 1.5 Hz, J = 8.3 Hz, 1H), 6.99-7.05 (m, 2H),
6.85 (dd, J = 1.3 Hz, J = 7.8 Hz, 1H), 6.72-6.79 (m, 1H), 5.21
(dd, J = 3.1 Hz, J = 8.0 Hz, 1H), 3.84 (bs, NH), 3.33 (dd, J =
3.7 Hz, J = 13.6 Hz, 1H), 3.06 (dd, J = 8.6 Hz, J = 13.6 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ 171.32, 162.59, 144.26,
139.04, 135.23, 132.84, 128.99, 128.34, 128.29, 128.05, 127.42,
125.88, 121.48, 120.72, 119.07, 118.30, 118.0, 69.99, 36.52.
2,4-Diphenyl-2,3-dihydrobenzo[b][1,4]thiazepine (1)
(Table-1, Entry 1): Yellow solid; m.p.100-102 °C; 1H NMR
(400 MHz, CDCl3): δ 8.01-8.06 (m, 3H), 7.30-7.52 (m, 11H),
4.98 (dd, J = 4.8 Hz, J = 12.7 Hz, 1H), 3.31 (dd, J = 4.7 Hz,
J = 12.9 Hz, 1H), 3.07 (t, J = 12.6 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ 168.67, 152.42, 144.84, 137.65, 135.04, 128.81,
128.74, 128.60, 128.48, 128.42, 128.32, 127.82, 127.29,
126.00, 121.84, 60.47, 37.63.
2-[2-(3,4,5-Trimethoxyphenyl)-2,3-dihydrobenzo[b]-
[1,4]thiazepin-4-yl]phenol (5) (Table-1, Entry 5): Yellow
crystal; m.p.: 160-162 °C; 1H NMR (400 MHz, CDCl3): δ 14.51
(bs, OH), 7.66 (d, J = 8.2 Hz, 1H), 7.47-7.52 (m, 2H), 7.38-7.42
(m, 1H), 7.31 (d, J = 8.6 Hz, 1H), 7.21 (dt, J = 1.4 Hz, J = 8.4
Hz, 1H), 7.07 (d, J = 8.5 Hz, 1H), 6.87 (t, J = 8.2 Hz, 1H),
6.54 (s, 2H), 5.02 (dd, J = 4.7 Hz, J = 11.3 Hz, 1H), 3.83 (s,
3H), 3.77 (s, 6H), 3.38 (dd, J = 4.7 Hz, J = 12.9 Hz, 1H), 3.08
(t, J = 12.5 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 173.21,
162.72, 153.27, 148.89, 138.80, 134.99, 133.67, 130.11,
128.62, 126.29, 125.63, 124.67, 118.63, 118.61, 118.47,
103.30, 103.28, 60.84, 60.66, 56.02, 36.90; IR (ATR): 3001,
2926, 1589, 1455, 1243, 760 cm-1; HRMS (ESI): calculated
for C24H23NO4SH [M+H]+ 422.1381, found 422.1391; CHN
analysis: calculated for C24H23NO4S: C: 68.39; H: 5.50; N:
3.32; O: 15.18; S: 7.61. Found: C: 68.50; H: 5.64; N: 3.18.
2-[2-(Benzo[d][1,3]dioxol-5-yl)-2,3-dihydrobenzo-
[b][1,4]thiazepin-4-yl]phenol (6) (Table-1, Entry 6): Light
yellow solid; m.p.: 135-138 °C; 1H NMR (400 MHz, CDCl3):
δ 14.47 (bs, OH), 7.65 (dd, J = 1.3 Hz, J = 7.7 Hz, 1H), 7.58
(dd, J = 1.3 Hz, J = 7.9 Hz, 1H), 7.48 (dt, J = 1.3 Hz, J = 8.4
Hz, 1H), 7.38-7.41 (m, 1H), 7.31 (dd, J = 1.2 Hz, J = 8.0 Hz,
1H), 7.22 (dt, J = 1.4 Hz, J = 8.4 Hz, 1H), 7.07 (dd, J = 1.0
Hz, J = 8.3 Hz, 1H), 6.82-6.91 (m, 1H), 6.82 (d, J = 1.3 Hz,
1H), 6.72-6.78 (m, 2H), 5.96 (s, 2H), 5.0 (dd, J = 4.7 Hz, J =
12.2 Hz, 1H), 3.37 (dd, J = 5.0 Hz, J = 13.3 Hz, 1H), 3.02 (t,
J = 13.3 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 172.95,
162.85, 148.76, 148.09, 147.42, 137.95, 135.25, 133.74,
130.03, 128.40, 126.54, 125.77, 119.33, 118.77, 118.69,
101.34, 60.05, 37.20.
2-(2-Phenyl-2,3-dihydrobenzo[b][1,4]thiazepin-4yl)-
phenol (2) (Table-1, Entry 2):Yellow Crystal (recrystalized
from ethanol); m.p.: 149-151 °C; 1H NMR (400 MHz, CDCl3):
δ 14.49 (bs, OH), 7.65 (dd, J = 1.7 Hz, J = 8.0 Hz, 1H), 7.50
(dd, J = 1.7 Hz, J = 8.5 Hz, 1H), 7.49 (dt, J = 1.1 Hz, J = 8.0
Hz, 1H), 7.39-7.43 (m, 1H), 7.31-7.34 (m, 6H), 7.22 (dt, J =
1.3 Hz, J = 8.4 Hz, 1H), 7.07 (d, J = 8.4 Hz, 1H), 6.68-6.92
(m, 1H), 5.06 (dd, J = 4.7 Hz, J = 12.6 Hz, 1H), 3.41 (dd, J =
4.7 Hz, J = 13.3 Hz, 1H), 3.09 (t, J = 13.3 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ 173.13, 162.78, 148.83, 143.68, 135.21,
133.65, 129.95, 128.89, 128.36, 128.07, 126.41, 126.04,
125.66, 124.44, 118.68, 118.59, 118.29, 60.05, 36.89; IR
(ATR): 3055, 1596, 1445, 1194, 725, 737 cm-1.
2-[2-(4-Methoxyphenyl)-2,3-dihydrobenzo[b][1,4]-
thiazepin-4-yl]phenol (3) (Table-1, Entry 3): Yellow solid;
m.p.: 163-165 °C; 1H NMR (400 MHz, CDCl3): δ 14.52 (bs,
OH), 7.58 (dd, J = 1.6 Hz, J = 7.7 Hz, 1H), 7.58 (dd, J = 1.4
Hz, J = 7.9 Hz, 1H), 7.48 (dt, J = 1.6 Hz, J = 8.4 Hz, 1H),
7.38-7.43 (m, 1H), 7.19-7.32 (m, 4H), 7.07 (dd, J = 1.2 Hz, J
= 8.6 Hz, 1H), 6.84-6.92 (m, 3H), 5.04 (dd, J = 5.0 Hz, J =
2.1 Hz, 1H), 3.80 (s, 3H), 3.38 (dd, J = 5.0 Hz, J = 12.7 Hz,
1H), 3.05 (t, J = 12.7 Hz, 1H); 13C NMR (100 MHz, CDCl3):
δ 173.12, 162.31, 159.31, 135.19, 133.59, 129.86, 128.41,
127.20, 126.34, 125.62, 125.48, 124.42, 118.65, 118.55,
114.15, 59.67, 55.35, 37.07.
2-(2-p-Tolyl-2,3-dihydrobenzo[b][1,4]thiazepin-4-
yl)phenol (7) (Table-1, Entry 7):Yellow solid; m.p.: 152-154
°C; 1H NMR (400 MHz, CDCl3): δ 14.44 (bs, OH), 7.51-758
(m, 2H), 7.42 (dt, J = 1.6 Hz, J = 9.2 Hz, 1H), 7.34 (dt, J = 1.8
Hz, J = 9.5 Hz, 1H), 7.22-7.25 (m, 1H), 7.09-7.14 (m, 2H),
7.07 (d, J = 8.0 Hz, 2H), 7.0 (d, J = 7.9 Hz, 1H), 6.81-6.86
(m, 1H), 4.95 (dd, J = 4.6 Hz, J = 12.43 Hz, 1H), 3.29 (dd, J
= 4.6 Hz, J = 12.4 Hz, 1H), 3.0 (t, J = 12.4 Hz, 1H), 2.27 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 173.20, 162.73, 148.86,
141.00, 137.95, 135.30, 133.71, 129.60, 128.39, 125.97,
124.53, 118.73, 118.59, 59.95, 36.96, 21.16.
2-[2-(3,4-Dimethoxyphenyl)-2,3-dihydrobenzo[b][1,4]-
thiazepin-4-yl]phenol (4) (Table-1, Entry 4): Yellow solid;
m.p.: 161-162 °C; 1H NMR (400 MHz, CDCl3): δ 14.52 (bs,
OH), 7.65 (d, J = 7.8 Hz, 1H), 7.52 (d, J = 8.1 Hz, 1H), 7.47
(d, J = 8.1 Hz, 1H), 7.40 (t, J = 8.5 Hz, 1H), 7.32 (d, J = 8.1
Hz, 1H), 7.21 (dt, J = 1.3 Hz, J = 7.8 Hz, 2H), 7.07 (d, J = 7.8
Hz, 1H), 6.78 - 6.90 (m, 3H), 5.05 (dd, J = 4.9 Hz, J = 11.7
Hz, 1H), 3.87 (s, 3H), 3.77 (s, 3H), 3.38 (dd, J = 5.0 Hz, J =
12.9 Hz, 1H), 3.08 (t, J = 12.4 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ 173.20, 162.74, 149.04, 148.82, 136.81, 135.05,
133.62, 131.59, 130.87, 129.97, 128.58, 126.28, 125.58,
124.68, 118.61, 118.13, 115.20, 110.97, 109.45, 60.17, 55.94,
55.77, 36.99; IR (ATR):2920, 1565, 1419, 1266, 651 cm-1;
HRMS (ESI): calculated for C23H21 NO3SH [M+H]+ 392.1276,
found 392.1295; CHN analysis: calculated for C23H21NO3S:
2-[2-(4-Chlorophenyl)-2,3-dihydrobenzo[b][1,4]-
thiazepin-4-yl]phenol (8) (Table-1, Entry 8): Yellow solid;
m.p.: 160-162 °C; 1H NMR (400 MHz, CDCl3): δ 14.42 (bs,
OH), 7.63 (dd, J = 1.9 Hz, J = 8.1 Hz, 1H), 7.55 (dd, J = 1.7
Hz, J = 8.6 Hz, 1H), 7.5 (dt, J = 1.7 Hz, J = 9.0 Hz, 1H), 7.40-
7.44 (m, 1H), 7.29-7.33 (m, 4H), 7.20-7.24 (m, 2H), 7.08 (d, J
= 7.6 Hz, 1H), 6.89-6.30 (m, 1H), 5.02 (dd, J = 4.9 Hz, J = 12.2
Hz, 1H), 3.38 (dd, J = 4.7 Hz, J = 13.0 Hz, 1H), 3.04 (t, J = 12.8
Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 172.93, 162.95, 142.18,
135.09, 133.83, 130.16, 129.11, 128.42, 127.53, 126.69, 125.72,
123.44, 118.75, 118.63, 59.29, 36.89.
2-[2-(4-Fluorophenyl)-2,3-dihydrobenzo[b][1,4]thia-
zepin-4-yl]phenol (9) (Table-1, Entry 9):Yellow solid; m.p.:
150-152 °C; 1H NMR (400 MHz, CDCl3): δ 14.45 (bs, OH),
7.66 (d, J = 7.8 Hz, 1H), 7.57 (d, J = 7.8 Hz, 1H), 7.51 (dt, J =