Mechanistic insight into thermal 1,3- and 1,5-sulfonyl migrations of…
139.9, 133.9, 133.4, 129.2, 128.0, 127.4, 126.3, 124.8,
123.1, 117.4, 115.4, 115.0, 114.8, 114.1, 55.7 ppm; IR
(KBr): vꢀ = 3282, 2959, 1652, 1466, 1312, 1258,
1H), 7.85 (d, J = 8.7 Hz, 2H), 7.79 (d, J = 8.7 Hz, 2H),
7.49 (d, J = 8.5 Hz, 1H), 7.38 (s, 1H), 7.01 (t, J = 7.6 Hz,
1H), 6.90 (d, J = 7.5 Hz, 1H), 6.80 (t, J = 7.5 Hz, 1H),
6.74 (d, J = 8.5 Hz, 1H), 6.68 (d, J = 7.9 Hz, 1H), 2.09 (s,
3H) ppm; 13C NMR (101 MHz, DMSO-d6): d = 169.1,
146.2, 143.5, 139.9, 135.2, 133.7, 128.2, 127.9, 127.5,
126.3, 124.9, 123.1, 118.9, 117.4, 115.4, 115.0, 114.1,
24.1 ppm; IR (KBr): vꢀ = 3279, 3019, 1690, 1585, 1463,
1319, 1139 cm-1; HRMS (ESI): m/z calcd. for C20H17N2-
?
1155 cm-1; HRMS (ESI): m/z calcd. for C19H16NO3S2
370.0566 ([M ? H]?), found 370.0559.
1-(4-Chlorophenylsulfonyl)-10H-phenothiazine
(2k, C18H12ClNO3S2)
1
Yellow solid; yield: 32 mg (28 %); m.p.: 133–134 °C; H
NMR (400 MHz, CDCl3): d = 8.66 (s, 1H), 7.84 (d,
J = 8.5 Hz, 2H), 7.53 (d, J = 8.1 Hz, 1H), 7.48 (d,
J = 8.5 Hz, 2H), 7.07 (t, J = 6.2 Hz, 1H), 7.04 (t,
J = 7.5 Hz, 1H), 6.96–6.85 (m, 2H), 6.82 (t, J = 7.8 Hz,
1H), 6.66 (d, J = 7.8 Hz, 1H) ppm; 13C NMR (101 MHz,
CDCl3): d = 141.5, 140.3, 140.2, 139.3, 132.1, 129.8,
128.3, 128.1, 128.0, 126.7, 124.0, 122.4, 121.9, 121.7,
117.8, 115.8 ppm; IR (KBr): vꢀ = 3343, 1572, 1472, 1447,
1316, 1146, 771 cm-1; HRMS (ESI): m/z calcd. for
?
O3S2 397.0675 ([M ? H]?), found 397.0668.
1-(2,4,6-Trimethylphenylsulfonyl)-10H-phenothiazine
(2m, C21H19NO2S2)
1
Yellow solid; yield: 7 mg (6 %); m.p.: 144–145 °C; H
NMR (400 MHz, CDCl3): d = 8.82 (s, 1H), 7.06–7.00 (m,
2H), 6.98–6.93 (m, 4H), 6.87 (t, J = 7.5 Hz, 1H), 6.70 (t,
J = 7.8 Hz, 1H), 6.65 (d, J = 7.9 Hz, 1H), 2.61 (s, 6H), 2.31
(s, 3H) ppm; 13C NMR (101 MHz, CDCl3): d = 143.8,
141.4, 139.8, 139.8, 134.5, 132.3, 130.6, 127.8, 126.8, 126.5,
125.0, 123.6, 121.6, 121.1, 117.7, 115.9, 22.5, 21.0 ppm; IR
(KBr): vꢀ = 3327, 2971, 2911, 1601, 1450, 1437, 1296,
?
C18H13ClNO2S2 374.0071 ([M ? H]?), found 374.0065.
3-(4-Chlorophenylsulfonyl)-10H-phenothiazine
?
1133 cm-1; HRMS (ESI): m/z calcd. for C21H20NO2S2
382.0930 ([M ? H]?), found 382.0924.
(3k, C18H12ClNO3S2)
1
Yellow solid; yield: 54 mg (48 %); m.p.: 231–233 °C; H
NMR (400 MHz, DMSO-d6): d = 9.24 (s, 1H), 7.93 (d,
J = 8.5 Hz, 2H), 7.67 (d, J = 8.5 Hz, 2H), 7.52 (dd,
J = 8.4, 1.9 Hz, 1H), 7.43 (s, 1H), 7.01 (d, J = 7.4 Hz,
1H), 6.91 (d, J = 7.5 Hz, 1H), 6.83 (d, J = 7.4 Hz, 1H),
6.75 (d, J = 8.5 Hz, 1H), 6.68 (d, J = 7.8 Hz, 1H) ppm;
13C NMR (101 MHz, DMSO-d6): d = 146.7, 140.8, 139.7,
138.3, 132.3, 129.7, 128.9, 127.99, 127.97, 126.3, 125.3,
123.2, 117.6, 115.4, 115.1, 114.2 ppm; IR (KBr):
3-(2,4,6-Trimethylphenylsulfonyl)-10H-phenothiazine
(3m, C21H19NO2S2)
1
Yellow solid; yield: 52 mg (46 %); m.p.: 234–236 °C; H
NMR (400 MHz, DMSO-d6): d = 9.19 (s, 1H), 7.37 (dd,
J = 8.5, 1.9 Hz, 1H), 7.20 (d, J = 1.7 Hz, 1H), 7.04 (s,
2H), 7.06–6.98 (m, 1H), 6.89 (d, J = 7.6 Hz, 1H), 6.80 (t,
J = 7.5 Hz, 1H), 6.75 (d, J = 8.5 Hz, 1H), 6.69 (d,
J = 7.8 Hz, 1H), 2.53 (s, 6H), 2.26 (s, 3H) ppm; 13C
NMR (101 MHz, DMSO-d6): d = 146.0, 142.9, 140.0,
138.9, 134.9, 134.3, 132.1, 127.9, 126.6, 126.3, 123.8,
123.0, 117.1, 115.4, 115.0, 113.9, 22.3, 20.4 ppm; IR
(KBr): vꢀ = 3285, 2959, 2905, 1661, 1593, 1471, 1318,
vꢀ = 3269, 1671, 1559, 1469, 1325, 1155, 755 cm-1
;
?
HRMS (ESI): m/z calcd. for C18H13ClNO2S2 374.0071
([M ? H]?), found 374.0069.
N-[4-(10H-Phenothiazine-1-sulfonyl)phenyl]acetamide
1159 cm-1; HRMS (ESI): m/z calcd. for C21H20NO2S2
382.0930 ([M ? H]?), found 382.0929.
?
(2l, C20H16N2O3S2)
1
Yellow solid; yield: 22 mg (18 %); m.p.: 131–132 °C; H
NMR (400 MHz, CDCl3): d = 8.64 (s, 1H), 7.81 (d,
J = 8.6 Hz, 2H), 7.70 (s, 1H), 7.66 (d, J = 8.5 Hz, 2H),
7.52 (d, J = 8.0 Hz, 1H), 7.03 (dd, J = 16.7, 7.7 Hz, 2H),
6.90 (d, J = 6.9 Hz, 1H), 6.88–6.83 (m, 1H), 6.80 (t,
J = 7.8 Hz, 1H), 6.64 (d, J = 7.8 Hz, 1H), 2.17 (s, 3H)
ppm; 13C NMR (101 MHz, CDCl3): d = 168.7, 142.8,
141.2, 139.4, 135.9, 131.8, 128.1, 127.9, 126.5, 123.8,
123.1, 121.7, 121.6, 119.5, 117.7, 115.8, 24.7 ppm; IR
(KBr): vꢀ = 3346, 2923, 2843, 1703, 1665, 1597, 1444,
1322, 1139 cm-1; HRMS (ESI): m/z calcd. for C20H17N2-
1-(2-Naphthalenylsulfonyl)-10H-phenothiazine
(2n, C22H15NO2S2)
1
Yellow solid; yield: 46 mg (39 %); m.p.: 168–170 °C; H
NMR (400 MHz, CDCl3): d = 8.81 (s, 1H), 8.52 (s, 1H),
7.97 (d, J = 7.9 Hz, 1H), 7.92 (d, J = 8.5 Hz, 1H), 7.86
(d, J = 7.6 Hz, 1H), 7.80 (dd, J = 8.7, 1.4 Hz, 1H), 7.66–
7.57 (m, 3H), 7.05 (d, J = 7.2 Hz, 1H), 7.03–6.98 (m, 1H),
6.89 (d, J = 6.5 Hz, 1H), 6.86 (d, J = 7.2 Hz, 1H), 6.84–
6.78 (m, 1H), 6.71 (d, J = 7.9 Hz, 1H) ppm; 13C NMR
(101 MHz, CDCl3): d = 141.5, 139.5, 138.4, 135.1, 132.1,
131.9, 129.9, 129.4, 129.3, 128.2, 128.2, 127.9, 127.8,
127.8, 126.6, 123.8, 122.9, 121.8, 121.7, 121.6, 117.8,
115.8 ppm; IR (KBr): vꢀ = 3344, 1562, 1444, 1435, 1309,
O3S2 397.0675 ([M ? H]?), found 397.0671.
?
N-[4-(10H-Phenothiazine-3-sulfonyl)phenyl]acetamide
(3l, C20H16N2O3S2)
1
?
1146 cm-1; HRMS (ESI): m/z calcd. for C22H16NO2S2
390.0617 ([M ? H]?), found 390.0623.
Yellow solid; yield: 51 mg (43 %); m.p.: 276–278 °C; H
NMR (400 MHz, DMSO-d6): d = 10.37 (s, 1H), 9.19 (s,
123