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K. N. Singh et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3): δ = 7.05 (d, J = 8.7 Hz, 2 H, HAr), 6.71 (d, J =
8.6 Hz, 2 H, HAr), 6.46 (s, 1 H, HAr), 5.98 (s, 1 H, HAr), 4.60 (t, J = 4.7 Hz,
1 H, ArCHAr), 3.88 (s, 3 H, OCH3), 3.82 (s, 3 H, OCH3), 3.62 (s, 3 H,
OCH3), 3.20–3.00 (m, 2 H, CH2), 2.98–2.87 (m, 1 H, CH2), 2.85–2.77 (m,
2 H, CH2), 2.66–2.50 (m, 1 H, CH2), 2.40 (s, 3 H, NCH3).
13C NMR (100 MHz, CDCl3): δ = 158.6, 147.6, 146.2, 135.6, 130.4,
130.3, 126.1, 113.3, 113.0, 110.8, 63.8, 57.4, 55.2, 54.7, 51.1, 47.0,
37.8.
IR (neat): 2940, 2834, 1507, 1252, 1027 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 6.68–6.61 (m, 3 H, HAr), 6.46 (s, 1 H,
HAr), 6.04 (s, 1 H, HAr), 5.84 (d, J = 1.1 Hz, 1 H, OCH2O), 5.83 (d, J = 1.2
Hz, 1 H, OCH2O), 4.47 (t, J = 4.8 Hz, 1 H, ArCHAr), 3.80 (s, 3 H, OCH3),
3.55 (s, 3 H, OCH3), 3.21–3.00 (m, 2 H, CH2), 2.98–2.87 (m, 1 H, CH2),
2.85–2.77 (m, 2 H, CH2), 2.62–2.48 (m, 1 H, CH2), 2.39 (s, 3 H, NCH3).
13C NMR (100 MHz, CDCl3): δ = 147.8, 147.4, 146.8, 146.4, 138.0,
130.3, 126.3, 122.7, 113.1, 111.0, 109.3, 107.3, 100.7, 62.1, 57.1, 55.6,
55.6, 51.3, 47.3, 37.0.
Anal. Calcd for C20H25NO3: C, 73.37; H, 7.70; N, 4.28. Found: C, 73.69;
H, 7.70; N, 4.37.
Anal. Calcd for C20H23NO4: C, 70.36; H, 6.79; N, 4.10. Found: C, 70.83;
H, 6.87; N, 4.34.
7,8-Dimethoxy-1-(3-methoxyphenyl)-3-methyl-2,3,4,5-tetrahy-
dro-1H-3-benzazepine (1c)
3-Methyl-7,8-(methylenedioxy)-1-phenyl-2,3,4,5-tetrahydro-1H-
Yellow oil; yield: 108 mg (30%).
3-benzazepine (1g)
IR (neat): 2964, 2894, 1540, 1206, 1073 cm–1
.
Light yellow oil; yield: 80 mg (26%).
1H NMR (400 MHz, CDCl3): δ = 7.09 (t, J = 7.6 Hz, 1 H, HAr), 6.75 (d, J =
7.6 Hz, 1 H, HAr), 6.70–6.67 (m, 2 H, HAr), 6.47 (s, 1 H, HAr), 6.01 (s, 1 H,
HAr), 4.55 (t, J = 4.7 Hz, 1 H, ArCHAr), 3.87 (s, 3 H, OCH3), 3.81 (s, 3 H,
OCH3), 3.61 (s, 3 H, OCH3), 3.22–3.04 (m, 2 H, CH2), 2.96–2.70 (m, 3 H,
CH2), 2.60–2.49 (m, 1 H, CH2), 2.39 (s, 3 H, NCH3).
13C NMR (100 MHz, CDCl3): δ = 159.7, 147.4, 146.4, 130.1, 128.9,
126.1, 122.0, 114.5, 113.1, 111.7, 111.0, 109.3, 62.2, 57.0, 55.6, 54.9,
50.4, 46.4, 37.2.
IR (neat): 2951, 2718, 1497, 1224, 1093 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.28–7.24 (m, 2 H, HAr), 7.22–7.19 (m,
3 H, HAr), 6.51 (s, 1 H, HAr), 6.03 (s, 1 H, HAr), 5.78 (d, J = 1.4 Hz, 1 H,
OCH2O), 5.75 (d, J = 1.4 Hz, 1 H, OCH2O), 4.50 (t, J = 4.8 Hz, 1 H,
ArCHPh), 3.22–3.07 (m, 2 H, CH2), 2.99–2.78 (m, 3 H, CH2), 2.64–2.49
(m, 1 H, CH2), 2.39 (s, 3 H, NCH3).
13C NMR (100 MHz, CDCl3): δ = 145.8, 145.7, 144.0, 131.5, 129.5,
128.3, 127.3, 126.3, 108.4, 107.8, 100.4, 62.1, 57.3, 51.3, 47.3, 37.3.
HRMS (ESI): m/z [M + H]+ calcd for C20H26NO3: 328.1907; found:
328.1932.
HRMS (ESI): m/z [M + H]+ calcd for C18H20NO2: 282.1488; found:
282.1407.
7,8-Dimethoxy-1-(3,4-dimethoxyphenyl)-3-methyl-2,3,4,5-tetra-
1-(4-Methoxyphenyl)-3-methyl-7,8-(methylenedioxy)-2,3,4,5-tet-
rahydro-1H-3-benzazepine (1h)
hydro-1H-3-benzazepine (1d)6b
Yellow pasty mass; yield: 92 mg (23%).
IR (neat): 2945, 2843, 1509, 1225, 1072 cm–1
Light brown solid; yield: 95 mg (28%); mp 90–92 °C.
.
IR (neat): 2934, 2831, 1479, 1274, 1039 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 6.75–6.69 (m, 2 H, HAr), 6.65 (d, J = 1.6
Hz, 1 H, HAr), 6.48 (s, 1 H, HAr), 6.02 (s, 1 H, HAr), 4.50 (t, J = 4.8 Hz, 1 H,
ArCHAr), 3.88 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3), 3.71 (s, 3 H, OCH3),
3.62 (s, 3 H, OCH3), 3.28–3.03 (m, 2 H, CH2), 2.98–2.81 (m, 2 H, CH2),
2.80–2.73 (m, 1 H, CH2), 2.62–2.50 (m, 1 H, CH2), 2.42 (s, 3 H, NCH3).
13C NMR (100 MHz, CDCl3): δ = 148.9, 148.2, 147.7, 146.2, 130.0,
125.9, 121.8, 120.6, 112.7, 111.6, 110.9, 110.0, 63.8, 57.3, 55.6, 55.4,
50.2, 47.4, 37.5.
1H NMR (400 MHz, CDCl3): δ = 7.11 (d, J = 8.6 Hz, 2 H, HAr), 6.79 (d, J =
8.7 Hz, 2 H, HAr), 6.51 (s, 1 H, HAr), 6.04 (s, 1 H, HAr), 5.80 (d, J = 1.5 Hz,
1 H, OCH2O), 5.78 (d, J = 1.4 Hz, 1 H, OCH2O), 4.60 (t, J = 4.7 Hz, 1 H,
ArCHAr), 3.82 (s, 3 H, OCH3), 3.20–3.00 (m, 2 H, CH2), 2.98–2.85 (m, 1
H, CH2), 2.83–2.77 (m, 2 H, CH2), 2.66–2.50 (m, 1 H, CH2), 2.40 (s, 3 H,
NCH3).
13C NMR (100 MHz, CDCl3): δ = 158.9, 145.8, 145.7, 135.9, 131.9,
130.5, 127.4, 113.7, 108.4, 107.8, 100.5, 62.3, 57.1, 55.1, 52.4, 47.3,
37.1.
7,8-Dimethoxy-1-(3,4,5-trimethoxyphenyl)-3-methyl-2,3,4,5-tet-
rahydro-1H-3-benzazepine (1e)
Anal. Calcd for C19H21NO3: C, 73.29; H, 6.80; N, 4.50. Found: C, 73.72;
H, 6.71; N, 4.43.
White solid; yield: 107 mg (25%); mp 142–144 °C.
IR (neat): 2935, 2863, 1469, 1245, 1012 cm–1
.
1-(3-Methoxyphenyl)-3-methyl-7,8-(methylenedioxy)-2,3,4,5-tet-
1H NMR (400 MHz, CDCl3): δ = 6.47 (s, 1 H, HAr), 6.40 (s, 2 H, HAr), 6.05
(s, 1 H, HAr), 4.53 (t, J = 4.8 Hz, 1 H, ArCHAr), 3.79 (s, 6 H, 2 OCH3), 3.70
(s, 6 H, 2 OCH3), 3.55 (s, 3 H, OCH3), 3.23–3.01 (m, 2 H, CH2), 2.98–2.75
(m, 3 H, CH2), 2.65–2.49 (m, 1 H, CH2), 2.40 (s, 3 H, NCH3).
13C NMR (100 MHz, CDCl3): δ = 153.4, 147.8, 146.2, 139.2, 137.1,
129.9, 126.0, 113.0, 110.9, 106.1, 62.0, 60.5, 57.1, 55.8, 55.6, 55.4,
51.1, 47.2, 37.1.
rahydro-1H-3-benzazepine (1i)
Brown oil; yield: 102 mg (30%).
IR (neat): 2941, 2840, 1489, 1239, 1051 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.09 (t, J = 7.6 Hz, 1 H, HAr), 6.75 (d, J =
7.6 Hz, 1 H, HAr), 6.70–6.67 (m, 2 H, HAr), 6.47 (s, 1 H, HAr), 6.01 (s, 1 H,
HAr), 5.82 (d, J = 1.4 Hz, 1 H, OCH2O), 5.79 (d, J = 1.4 Hz, 1 H, OCH2O),
4.40 (t, J = 4.8 Hz, 1 H, ArCHAr), 3.80 (s, 3 H, OCH3), 3.21–3.01 (m, 2 H,
CH2), 2.96–2.71 (m, 3 H, CH2), 2.62–2.48 (m, 1 H, CH2), 2.40 (s, 3 H,
NCH3).
Anal. Calcd for C22H29NO5: C, 68.20; H, 7.54; N, 3.61. Found: C, 68.82;
H, 7.58; N, 3.83.
13C NMR (100 MHz, CDCl3): δ = 159.6, 147.4, 146.6, 130.2, 128.5,
126.2, 122.1, 114.2, 113.0, 111.2, 111.0, 109.2, 100.5, 62.1, 57.1, 55.6,
51.4, 47.4, 37.1.
7,8-Dimethoxy-3-methyl-1-[3,4-(methylenedioxy)phenyl]-2,3,4,5-
tetrahydro-1H-3-benzazepine (1f)
HRMS (ESI): m/z [M + H]+ calcd for C19H22NO3: 312.1599; found:
Light yellow solid; yield: 111 mg (29%); mp 119–122 °C.
312.1591.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 3212–3220