J. K. Laha, S. Sharma, N. Dayal
FULL PAPER
13C NMR: δ = 140.0, 132.5, 129.1, 127.0, 44.9, 22.9, 11.0 ppm.
HRMS: calcd. for C9H14NO2S [M
200.0740.
128.4, 128.3, 56.0, 39.0 ppm. HRMS: calcd. for C14H13ClNO2S [M
+ H]+ 294.0356; found 294.0346.
+
H]+ 200.0745; found
1-Fluoro-6-methyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Dioxide
(12): Off-white solid (120 mg, 87%); m.p. 140–142 °C. IR (KBr): ν
˜
N-Butylbenzenesulfonamide (5l): Viscous oil (104 mg, 98%). IR
= 3351, 3088, 2817, 1448, 1338, 1186, 704 cm–1. 1H NMR: δ = 7.82
(dd, J = 7.6, 0.4 Hz, 1 H), 7.60–7.57 (m, 1 H), 7.56–7.51 (m, 1 H),
7.51–7.44 (m, 4 H), 4.06 (s, 1 H), 3.53 (s, 1 H), 2.86 (s, 3 H) ppm.
13C NMR: δ = 160.3 (J = 250.9 Hz), 136.7, 134.0, 133.7, 130.5,
130.1 (J = 4.8 Hz), 129.7 (J = 8.5 Hz), 129.5, 128.9, 126.3, 126.2,
123.4 (J = 3.5 Hz), 121.1, 120.8, 56.0, 39.1 ppm. HRMS: calcd. for
C14H13FNO2S [M + H]+ 278.0651; found 278.0644.
1
(neat): ν = 3285, 2933, 2873, 1447, 1324, 1161, 1094, 755 cm–1. H
˜
NMR: δ = 7.91–7.88 (m, 2 H), 7.59 (tt, J = 7.4, 1.2 Hz, 1 H), 7.56–
7.50 (m, 2 H), 4.79 (br. s, 1 H), 2.93 (t, J = 7.0 Hz, 2 H), 1.47 (q,
J = 6.8 Hz, 2 H), 1.33 (q, J = 7.3 Hz, 2 H), 0.85 (t, J = 7.5 Hz, 3
H) ppm. 13C NMR: δ = 139.9, 132.5, 129.0, 127.0, 42.9, 31.5 ppm.
HRMS: calcd. for C10H16NO2S [M + H]+ 214.0902; found
214.0900.
6-Methyl-1-nitro-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Dioxide
N-Benzylbenzenesulfonamide (5m): Off-white solid (121 mg, 98%);
(13): Off-white solid (120 mg, 79%); m.p. 173–175 °C. IR (KBr): ν
˜
m.p. 122–124 °C. IR (KBr): ν = 3330, 2929, 1447, 1325, 1150, 1060,
˜
= 3435, 3084, 2924, 1531, 1439, 1345, 1170 cm–1. 1H NMR: δ =
8.23 (dd, J = 7.8, 1.3 Hz, 1 H), 8.05 (dd, J = 8.3, 1.3 Hz, 1 H), 7.73
(t, J = 8.0 Hz, 1 H), 7.53–7.42 (m, 3 H), 7.23 (d, J = 7.2 Hz, 1 H),
4.19 (d, J = 11.8 Hz, 1 H), 3.70 (d, J = 11.5 Hz, 1 H), 2.91 (s, 3 H)
ppm. 13C NMR: δ = 150.3, 137.5, 135.3, 132.8, 132.5, 130.8, 130.5,
130.3, 129.7, 129.3, 128.0, 127.9, 56.01, 39.12 ppm. HRMS: calcd.
for C14H13N2O4S [M + H]+ 305.0596; found 305.0590.
750 cm–1. 1H NMR: δ = 7.91–7.88 (m, 2 H), 7.61 (tt, J = 8.4,
2.3 Hz, 1 H), 7.55–7.51 (m, 2 H), 7.30–7.27 (m, 3 H), 7.23–7.19 (m,
2 H), 4.77 (t, J = 5.1 Hz, 1 H), 4.18 (d, J = 6.3 Hz, 2 H) ppm. 13C
NMR: δ = 139.9, 136.1, 132.7, 129.1, 128.7, 127.9, 127.8, 127.1,
47.3 ppm. HRMS: calcd. for C13H14NO2S [M + H]+ 248.0745;
found 248.0745.
N-(2-Bromobenzyl)-N-methylbenzenesulfonamide (7): Off-white so-
3-Methoxy-6-methyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Di-
oxide (14): Off-white solid (97 mg, 67%); m.p. 135–140 °C. IR
lid (133 mg, 78%); m.p. 66–68 °C. IR (KBr): ν = 3400, 2950, 2843,
˜
1454, 1345, 1053, 747 cm–1. 1H NMR: δ = 7.90–7.88 (m, 2 H),
7.68–7.54 (m, 5 H), 7.36 (dt, J = 7.5, 1.0 Hz, 1 H), 7.18 (dt, J =
7.8, 1.6 Hz, 1 H), 4.34 (s, 2 H), 2.72 (s, 3 H) ppm. 13C NMR: δ =
137.5, 134.9, 132.8, 129.8, 129.3, 129.2, 127.9, 127.4, 123.4, 53.5,
35.0 ppm. HRMS: calcd. for C14H15BrNO2S [M + H]+ 340.0007;
found 340.0001.
(KBr): ν = 3400, 2923, 2852, 1604, 1478, 1337, 116 cm–1. 1H NMR:
˜
δ = 7.55 (d, J = 6.4 Hz, 1 H), 7.53 (s, 1 H), 7.52–7.47 (m, 1 H),
7.45–7.38 (m, 3 H), 7.25 (dd, J = 8.3, 2.8 Hz, 1 H), 3.94 (s, 3 H),
3.80 (s, 2 H), 2.91 (s, 3 H) ppm. 13C NMR: δ = 159.4, 140.7, 135.9,
133.3, 131.5, 131.1, 130.1, 129.6, 128.4, 128.3, 119.4, 112.1, 56.2,
55.8, 39.0 ppm. HRMS: calcd. for C15H16NO3S [M
290.0851; found 290.0848.
+
H]+
2,6-Dimethyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Dioxide (8):
Off-white solid (98 mg, 72%); m.p. 112–114 °C. IR (KBr): ν =
˜
1,6-Dimethyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Dioxide and
3,6-Dimethyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Dioxide
1
3284, 2923, 2853, 1461, 1335, 1160 cm–1. H NMR: δ = 7.90 (d, J
= 7.9 Hz, 1 H), 7.53–7.47 (m, 2 H), 7.44–7.42 (m, 3 H), 7.38 (d, J
= 8.0 Hz, 1 H), 3.77 (s, 2 H), 2.88 (s, 3 H), 2.53 (s, 3 H) ppm. 13C
NMR: δ = 144.0, 140.9, 139.3, 133.5, 132.0, 130.5, 130.1, 129.4,
128.9, 128.8, 128.3, 127.6, 56.2, 38.9, 21.6 ppm. HRMS: calcd. for
C15H16NO2S [M + H]+ 274.0902; found 274.0901.
Mixture (15): Off-white solid (102 mg, 75%); m.p. 147–150 °C. IR
(KBr): ν = 3400, 2923, 2852, 1463, 1338, 1163, 749 cm–1. 1H NMR:
˜
δ = 7.86 (d, J = 7.7 Hz, 1 H), 7.80 (s, 0.6 H), 7.59 (d, J = 7.7 Hz,
1 H), 7.50–7.36 (m, 9 H), 4.01 (d, J = 11.4 Hz, 1 H), 3.76 (s, 1 H),
3.42 (d, J = 11.3 Hz, 1 H), 2.87 (s, 2 H), 2.78 (s, 3 H), 2.49 (s, 2
H), 2.42 (s, 3 H) ppm. 13C NMR: δ = 140.9, 138.9, 138.7, 137.4,
137.1, 136.5, 135.6, 135.0, 134.6, 133.9, 133.7, 133.4, 130.2, 130.1,
130.0, 129.8, 129.4, 128.1, 128.7, 128.7, 128.5, 128.3, 127.8, 125.2,
56.2, 39.0, 29, 21.1, 20.8 ppm. HRMS: calcd. for C15H16NO2S [M
+ H]+ 274.0902; found 274.0892.
2-Methyl-6-propyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Diox-
ide (9): Semisolid (102 mg, 68%). IR (neat): ν = 3436, 2925, 2854,
˜
1458, 1335, 1160, 1015, 753 cm–1. 1H NMR: δ = 7.90 (d, J = 8.0 Hz,
1 H), 7.50–7.48 (m, 2 H), 7.43–7.41 (m, 3 H), 7.36 (d, J = 8.0,
1.1 Hz, 1 H), 3.86 (s, 2 H), 3.27 (t, J = 7.4 Hz, 2 H), 2.52 (s, 3 H),
1.75–1.65 (m, 2 H), 1.00 (t, J = 7.3 Hz, 3 H) ppm. 13C NMR: δ =
143.6, 140.9, 139.1, 134.0, 133.9, 130.3, 130.0, 129.2, 128.9, 128.4,
126.8, 53.3, 53.3, 21.5, 21.0, 11.2 ppm. HRMS: calcd. for
C17H20NO2S [M + H]+ 302.1215; found 302.1211.
6-Methyl-4-(trifluoromethyl)-6,7-dihydrodibenzo[d,f][1,2]thiazepine
5,5-Dioxide (16): Off-white solid (74 mg, 45%); m.p. 82–85 °C. IR
1
(KBr): ν = 3340, 2925, 2853, 1455, 1359, 1312, 1176, 763 cm–1. H
˜
NMR: δ = 8.00 (dd, J = 6.8, 2.2 Hz, 1 H), 7.82–7.77 (m, 2 H), 7.54
(dt, J = 7.3, 1.6 Hz, 1 H), 7.48–7.41 (m, 3 H), 3.81 (s, 2 H), 3.02
(s, 3 H) ppm. 13C NMR: δ = 143.3, 142.0, 135.0, 133.1, 132.0,
129.6, 129.5, 129.2, 128.5, 127.5 (q, J = 7 Hz), 123.8 (q, J =
273 Hz), 120.6, 55.6, 39.3 ppm. HRMS: calcd. for C15H13F3NO2S
[M + H]+ 328.0619; found 328.0617.
6-Butyl-2-methyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Dioxide
(10): Off-white solid (86 mg, 55%); m.p. 127–128 °C. IR (KBr): ν
˜
1
= 3301, 2952, 2866, 1465, 1330, 1165, 1094, 773 cm–1. H NMR: δ
= 7.87 (d, J = 7.8 Hz, 1 H), 7.48–7.46 (m, 2 H), 7.41–7.39 (m, 3
H), 7.33 (td, J = 8.0, 0.9 Hz, 1 H), 3.83 (s, 2 H), 3.26 (t, J = 7.4 Hz,
2 H), 2.49 (s, 3 H), 1.70–1.59 (m, 2 H), 1.44–1.35 (m, 2 H), 0.95 (t,
J = 7.4 Hz, 3 H) ppm. 13C NMR: δ = 143.6, 140.9, 139.1, 134.0,
133.9 130.3, 130.0, 129.2, 128.8, 128.4, 126.8, 53.2, 51.3, 29.7, 21.5,
6-Methyl-6,7-dihydro-[1,3]dioxolo[4Ј,5Ј:4,5]benzo[1,2d]benzo[f]-
[1,2]thiazepine 5,5-Dioxide (17): Off-white solid (96 mg, 64%); m.p.
1
160–162 °C. IR (KBr): ν = 3428, 3232, 2917, 1604, 1440 cm–1. H
˜
20.0, 13.7 ppm. HRMS: calcd. for C18H22NO2S [M
316.1371; found 316.1367.
+
H]+
NMR: δ = 8.01 (dd, J = 8.2, 0.9 Hz, 1 H), 7.71 (dt, J = 8.1, 1.3 Hz,
1 H), 7.56–7.52 (m, 2 H), 6.93 (d, J = 7.7 Hz, 2 H), 6.06 (s, 2 H),
3.66 (s, 2 H), 2.86 (s, 3 H) ppm. 13C NMR: δ = 148.6, 148.1, 139.4,
134.7, 134.5, 133.2, 129.6, 128.0, 127.5, 127.2, 110.6, 108.9, 101.7,
55.8, 38.8 ppm. HRMS: calcd. for C15H14NO4S [M + H]+
304.0644; found 304.0643.
2-Chloro-6-methyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Diox-
ide (11): Off-white solid (95 mg, 65%); m.p. 150–152 °C. IR (KBr):
1
ν = 3289, 2927, 1443, 1386, 1168 cm–1. H NMR: δ = 7.95 (d, J =
˜
8.3 Hz, 1 H), 7.62 (d, J = 2.0 Hz, 1 H), 7.57–7.50 (m, 2 H), 7.50–
7.43 (m, 3 H), 3.81 (s, 2 H), 2.90 (s, 3 H) ppm. 13C NMR: δ = 6-Propyl-6,7-dihydrodibenzo[d,f][1,2]thiazepine 5,5-Dioxide (18):
141.0, 139.6, 139.4, 133.4, 133.3, 130.4, 129.8, 129.6, 129.6, 128.9,
Off-white solid (116 mg, 81%); m.p. 92–95 °C. IR (KBr): ν = 3153,
˜
7890
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Eur. J. Org. Chem. 2015, 7885–7891