The Journal of Organic Chemistry
Article
CDCl3): δ 168.6, 144.6, 135.7, 134.9, 133.3, 132.6, 130.8, 117.1, 98.3,
36.3, 30.7, 29.6. HRMS (ESI) m/z: (M + H)+ calcd for C11H11INO (M
+ H), 299.9885; found (M + H), 299.9883.
114−115 °C; Rf (30% EtOAc/petroleum ether) 0.4; IR (neat, cm−1):
1725, 1630, 1569; 1H NMR (400 MHz, CDCl3): δ 7.24 (s, 1H), 5.98
(d, J = 7.5 Hz, 1H), 5.62 (q, J = 7.4 Hz, 1H), 3.91 (s, 3H), 3.87 (s, 3H),
3.83 (s, 3H), 3.29 (s, 3H), 3.24 (d, J = 7.3 Hz, 2H). 13C {1H} NMR
(100 MHz, CDCl3): δ 168.9, 151.3, 148.0, 144.9, 130.8, 130.2, 129.2,
117.9, 109.7, 61.4, 60.8, 55.9, 36.3, 22.0. HRMS (ESI) m/z: (M + Na)+
calcd for C14H17NO4Na (M + Na), 286.1055; found (M + Na),
286.1055.
5.3.14. 2,5-Dihydro-1H-benzo[c]azepin-1-one (3ma). Prepared as
shown in the general experimental procedure (a). Yellow sticky liquid;
yield(25 mg, 73%); Rf (30% EtOAc/petroleum ether) 0.5; IR (neat,
cm−1): 3447, 1672, 1639, 1569; 1H NMR (400 MHz, CDCl3): δ 8.27
(s, 1H), 8.00−7.85 (m, 1H), 7.45 (td, J = 7.5, 1.3 Hz, 1H), 7.33 (dd, J =
11.0, 4.2 Hz, 1H), 7.13 (d, J = 7.6 Hz, 1H), 6.11 (dd, J = 7.5, 4.3 Hz,
1H), 5.57 (q, J = 7.1 Hz, 1H), 3.32 (d, J = 6.9 Hz, 2H). 13C {1H} NMR
(100 MHz, CDCl3): δ 170.8, 142.4, 132.7, 132.5, 130.9, 126.9, 126.6,
124.9, 115.9, 31.5. HRMS (ESI) m/z: (M + H)+ calcd for C10H10NO
(M + H), 160.0762; found (M + H), 160.0762.
5.3.7. 6-Methoxy-2-methyl-2,5-dihydro-1H-benzo[c]azepin-1-
one (3ga). Prepared as shown in the general experimental procedure
(a). Sticky liquid; yield(19.6 mg, 44%); Rf (20% EtOAc/petroleum
1
ether) 0.7; IR (neat, cm−1): 1723, 1632, 1576; H NMR (400 MHz,
CDCl3): δ 7.44 (d, J = 7.8 Hz, 1H), 7.21 (t, J = 8.0 Hz, 1H), 6.96 (d, J =
8.1 Hz, 1H), 5.98 (d, J = 7.3 Hz, 1H), 5.62 (q, J = 7.4 Hz, 1H), 3.83 (s,
3H), 3.29 (m, 5H). 13C {1H} NMR (100 MHz, CDCl3): δ 169.4, 153.9,
135.4, 132.3, 130.9, 126.6, 122.8, 118.1, 113.0, 55.9, 36.2, 21.7. HRMS
(ESI) m/z: (M + H)+ calcd for C12H14NO2 (M + H), 204.1025; found
(M + H), 204.1025.
5.3.8. 8-Methoxy-2-methyl-2,5-dihydro-1H-benzo[c]azepin-1-
one (3ga′). Prepared as shown in the general experimental procedure
(a). Sticky liquid; yield(8.2 mg, 18%); Rf (20% EtOAc/petroleum
1
ether) 0.6; IR (neat, cm−1): 1723, 1632, 1576; H NMR (400 MHz,
CDCl3): δ 7.44 (d, J = 7.8 Hz, 1H), 7.21 (t, J = 8.0 Hz, 1H), 6.96 (d, J =
8.1 Hz, 1H), 5.98 (d, J = 7.3 Hz, 1H), 5.62 (q, J = 7.4 Hz, 1H), 3.83 (s,
3H), 3.30 (d, J = 7.7 Hz, 2H), 3.30−3.16 (S, 3H). 13C {1H} NMR (100
MHz, CDCl3): δ 169.5, 153.9, 135.4, 132.3, 130.9, 126.6, 122.8, 118.1,
113.0, 55.9, 36.2, 21.7. HRMS (ESI) m/z: (M + H)+ calcd for
C12H14NO2 (M + H), 204.1025; found (M + H), 204.1024.
5.3.15. 7-Methoxy-2,5-dihydro-1H-benzo[c]azepin-1-one (3na).
Prepared as shown in the general experimental procedure (a). Yellow
sticky solid; yield(29 mg, 69%); Rf (30% EtOAc/petroleum ether)
1
0.3; IR (neat, cm−1): 2961, 1740, 1642, 1565; H NMR (400 MHz,
CDCl3): δ 7.90 (d, J = 8.7 Hz, 1H), 7.46 (s, 1H), 6.84 (dd, J = 8.6, 2.4
Hz, 1H), 6.62 (d, J = 2.3 Hz, 1H), 6.08 (dd, J = 7.5, 4.4 Hz, 1H), 5.52 (q,
J = 7.1 Hz, 1H), 3.84 (s, 3H), 3.29 (d, J = 6.9 Hz, 2H). 13C {1H} NMR
(100 MHz, CDCl3): δ 169.8, 163.0, 144.0, 133.2, 125.3, 125.2, 115.1,
112.2, 111.9, 55.3, 31.9. HRMS (ESI) m/z: (M + H)+ calcd for
C11H12NO2 (M + H), 190.0868; found (M + H), 190.0871.
5.3.9. 8-Bromo-2-methyl-2,5-dihydro-1H-benzo[c]azepin-1-one
(3ha) & 6-Bromo-2-methyl-2,5-dihydro-1H-benzo[c]azepin-1-one
(3ha′). Prepared as shown in the general experimental procedure (a).
Inseparable mixture, sticky liquid; yield(38.5 mg, 76%); Rf (20%
1
EtOAc/petroleum ether) 0.5; IR (neat, cm−1): 1725, 1630, 1589; H
NMR (400 MHz, CDCl3): δ 7.99 (d, J = 2.1 Hz, 1H), 7.83−7.72 (m,
1H), 7.64 (dd, J = 8.0, 1.1 Hz, 1H), 7.48 (dd, J = 8.1, 2.1 Hz, 1H), 7.12
(t, J = 7.9 Hz, 1H), 6.95 (d, J = 8.1 Hz, 1H), 6.02 (d, J = 7.4 Hz, 1H),
5.96 (d, J = 7.6 Hz, 1H), 5.70−5.60 (m, 2H), 3.47 (d, J = 7.4 Hz, 2H),
3.29 (s, 3H), 3.28 (s, 3H), 3.17 (d, J = 7.1 Hz, 2H). 13C {1H} NMR
(100 MHz, CDCl3): δ 168.5, 167.8, 142.1, 142.0, 135.9, 135.5, 135.2,
134.2, 133.8, 131.0, 130.6, 130.3, 127.7, 127.4, 120.6, 120.1, 117.4,
116.8, 36.3, 36.2, 30.6, 29.6. HRMS (ESI) m/z: (M + H)+ calcd for
C11H11BrNO (M + H), 252.0024; found (M + H), 252.0027.
5.3.10. 2,8-Dimethyl-2,5-dihydro-1H-benzo[c]azepin-1-one (3ia).
Prepared as shown in the general experimental procedure (a). Sticky
liquid; yield(30 mg, 80%); Rf (20% EtOAc/petroleum ether) 0.6; IR
(neat, cm−1): 1724, 1633, 1569; 1H NMR (400 MHz, CDCl3): δ 7.68
(s, 1H), 7.18 (d, J = 6.8 Hz, 1H), 6.95 (d, J = 7.7 Hz, 1H), 5.94 (d, J =
7.6 Hz, 1H), 5.63 (q, J = 7.3 Hz, 1H), 3.28 (s, 3H), 3.18 (d, J = 7.1 Hz,
2H), 2.34 (s, 3H). 13C {1H} NMR (100 MHz, CDCl3): δ 169.5, 140.5,
136.1, 133.5, 132.2, 131.5, 130.4, 125.9, 117.9, 36.3, 30.7, 20.8. HRMS
(ESI) m/z: (M + H)+ calcd for C12H14NO (M + H), 188.1075; found
(M + H), 188.1077.
5.3.11. 2,9-Dimethyl-2,5-dihydro-1H-benzo[c]azepin-1-one (3ja).
Prepared as shown in the general experimental procedure (a). Sticky
liquid; yield(27 mg, 63%); Rf (20% EtOAc/petroleum ether) 0.5; IR
(neat, cm−1): 1707, 1628, 1571; 1H NMR (400 MHz, CDCl3): δ 7.26
(s, 1H), 7.18 (t, J = 7.5 Hz, 1H), 7.10 (d, J = 7.6 Hz, 1H), 6.89 (d, J = 7.4
Hz, 1H), 5.93 (d, J = 7.3 Hz, 1H), 5.69 (q, J = 7.3 Hz, 1H), 3.28 (s, 3H),
2.43 (s, 3H). 13C {1H} NMR (100 MHz, CDCl3): δ 169.9, 144.7, 139.2,
132.9, 130.2, 129.6, 129.3, 123.2, 119.9, 35.4, 31.3, 21.2. HRMS (ESI)
m/z: (M + H)+ calcd for C12H14NO (M + H), 188.1075; found (M +
H), 188.1072.
5.3.16. 2-Methyl-2,5-dihydro-1H-naphtho[1,2-c]azepin-1-one
(3oa). Prepared as shown in the general experimental procedure (a).
Yellow sticky liquid; yield(31.2 mg, 66%); Rf (20% EtOAc/
1
petroleum ether) 0.9; IR (neat, cm−1): 1724, 1636, 1589; H NMR
(400 MHz, CDCl3): δ 8.38 (d, J = 8.6 Hz, 1H), 7.80 (t, J = 7.8 Hz, 2H),
7.50 (t, J = 7.7 Hz, 1H), 7.43 (t, J = 7.4 Hz, 1H), 7.19 (d, J = 8.4 Hz,
1H), 5.97 (d, J = 7.3 Hz, 1H), 5.78 (q, J = 7.2 Hz, 1H), 3.40 (s, 3H). 13C
{1H} NMR (100 MHz, CDCl3): δ 169.5, 142.9, 132.6, 131.9, 130.9,
130.3, 129.1, 128.0, 127.0, 125.8, 125.3, 124.5, 120.1, 35.7, 31.4. HRMS
(ESI) m/z: (M + H)+ calcd for C15H14NO (M + H), 224.1075; found
(M + H), 224.1072.
5.3.17. 2-Methyl-2,5-dihydro-1H-naphtho[2,3-c] azepin-1-one
(3pa). Prepared as shown in the general experimental procedure (a).
Yellow sticky liquid; yield(36.8 mg, 78%); Rf (20% EtOAc/
1
petroleum ether) 0.4; IR (neat, cm−1): 1712, 1643, 1565; H NMR
(400 MHz, CDCl3): δ 8.43 (s, 1H), 7.90 (d, J = 8.0 Hz, 1H), 7.77 (d, J =
8.1 Hz, 1H), 7.54−7.42 (m, 3H), 5.98 (d, J = 7.6 Hz, 1H), 5.71 (q, J =
7.3 Hz, 1H), 3.42 (d, J = 7.2 Hz, 2H), 3.33 (s, 3H). 13C {1H} NMR (100
MHz, CDCl3): δ 169.4, 140.3, 134.7, 132.7, 132.2, 131.7, 130.4, 128.9,
127.6, 126.8, 125.7, 123.6, 118.1, 36.3, 31.6. HRMS (ESI) m/z: (M +
H)+ calcd for C15H14NO (M + H), 224.1075; found (M + H),
224.1076.
5.3.18. N-(2-Methyl-1-oxo-2,5-dihydro-1H-benzo[c]azepin-7-yl)
acetamide (3qa). Prepared as shown in the general experimental
procedure (a). Colorless sticky liquid; yield(38.5 mg, 72%); Rf (30%
EtOAc/petroleum ether) 0.5; IR (neat, cm−1): 1727, 1662, 1610; 1H
NMR (400 MHz, CDCl3): δ 8.37 (s, 1H), 7.74 (d, J = 8.4 Hz, 1H), 7.57
(s, 1H), 7.16 (dd, J = 8.4, 1.5 Hz, 1H), 5.95 (d, J = 7.6 Hz, 1H), 5.60 (q,
J = 7.2 Hz, 1H), 3.27 (s, 3H), 3.15 (d, J = 7.1 Hz, 2H), 2.16 (s, 3H). 13C
{1H} NMR (100 MHz, CDCl3): δ 169.0, 144.3, 141.2, 131.9, 130.5,
128.9, 117.5, 117.1, 116.7, 36.3, 31.3, 24.5. HRMS (ESI) m/z: (M +
H)+ calcd for C13H15N2O2 (M + H), 231.1134; found (M + H),
231.1134.
5.3.12. 9-Chloro-2-methyl-2,5-dihydro-1H-benzo[c]azepin-1-one
(3ka). Prepared as shown in the general experimental procedure (a).
Yellow sticky liquid; yield(19.4 mg, 45%); Rf (30% EtOAc/
1
petroleum ether) 0.5; IR (neat, cm−1): 1707, 1632, 1587; H NMR
(400 MHz, CDCl3): δ 7.31 (d, J = 8.0 Hz, 1H), 7.21 (t, J = 7.8 Hz, 1H),
6.97 (d, J = 7.5 Hz, 1H), 5.96 (d, J = 7.4 Hz, 1H), 5.70 (q, J = 7.3 Hz,
1H), 3.30 (s, 3H). 13C {1H} NMR (100 MHz, CDCl3): δ 167.2, 146.8,
134.1, 132.3, 130.4, 130.4, 128.8, 124.0, 119.9, 35.4, 31.2. HRMS (ESI)
m/z: (M + Na)+ calcd for C11H10ClNONa (M + Na), 230.0349; found
(M + Na), 230.0349.
5.3.13. 6,7,8-Trimethoxy-2-methyl-2,5-dihydro-1H-benzo[c]-
azepin-1-one (3la). Prepared as shown in the general experimental
procedure (a). White solid; yield(42.9 mg, 71%); melting point
5.3.19. 7-Acetyl-2-methyl-2,5-dihydro-1H-benzo[c]azepin-1-one
(3ra). Prepared as shown in the general experimental procedure (a).
Yellow sticky liquid; yield(29.6 mg, 63%); Rf (30% EtOAc/
1
petroleum ether) 0.5; IR (neat, cm−1): 1685, 1630, 1562; H NMR
(400 MHz, CDCl3): δ 7.95 (d, J = 8.1 Hz, 1H), 7.84 (dd, J = 8.1, 1.5 Hz,
1H), 7.67 (s, 1H), 5.99 (d, J = 7.6 Hz, 1H), 5.66 (q, J = 7.3 Hz, 1H),
3.30 (d, 5H), 2.61 (s, 3H). 13C {1H} NMR (100 MHz, CDCl3): δ
197.6, 168.4, 143.6, 139.0, 137.8, 131.5, 130.6, 126.3, 125.7, 117.6, 36.3,
4633
J. Org. Chem. 2021, 86, 4625−4637