3.2. Synthesis of Adducts (Specific Spectral Reference Supplementary Materials)
3-Phenyl-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.74 (d, J = 0.6 Hz, 1H), 7.66–7.60 (m, 2H), 7.50–7.41 (m, 2H), 7.41–7.32 (m, 3H), 7.29 (dq, J = 7.7, 0.9 Hz, 1H), 7.25–7.19 (m, 1H). 13C-NMR (75 MHz, Chloroform-d) δ 160.55, 153.48, 139.83, 134.67, 131.36, 128.83, 128.49, 128.44, 128.33, 127.87, 124.46, 119.64, 116.42. GC-MS (EI, 70 ev): m/z (%) = 222 (M+, 100), 195 (14), 194 (93), 166 (12), 165 (89), 164 (16), 163 (10), 82 (11).
6-Methyl-3-phenyl-2H-chromen-2-one: 7u1H-NMR (300 MHz, Chloroform-d) δ 7.70 (s, 1H), 7.67–7.58 (m, 2H), 7.48–7.33 (m, 3H), 7.31–7.24 (m, 2H), 7.23–7.14 (m, 1H), 2.36 (s, 3H). 13C-NMR (75 MHz, Chloroform-d) δ 160.74, 151.61, 139.84, 134.81, 134.11, 132.40, 128.71, 128.48, 128.40, 128.14, 127.65, 119.36, 116.11, 20.76. GC-MS (EI, 70 ev): m/z (%) = 236 (M+, 100), 209 (10), 208 (67), 207 (62), 179 (24), 178 (40), 152 (16), 139 (10), 89 (12), 77 (13), 76 (12), 51 (11).
6-Fluoro-3-phenyl-2H-chromen-2-one: 1H-NMR (300 MHz, Chloroform-d) δ 7.75 (s, 1H), 7.73–7.67 (m, 2H), 7.50–7.41 (m, 3H), 7.35 (dddd, J = 8.8, 4.5, 1.8, 1.1 Hz, 1H), 7.29–7.19 (m, 2H). 13C-NMR (75 MHz, Chloroform-d) δ 160.17, 149.63, 138.73, 134.28, 129.52, 129.16, 128.54, 128.53, 120.28, 118.76 (d, J = 24.6 Hz), 118.05, 117.94, 113.05 (d, J = 23.9 Hz). GC-MS (EI, 70 ev): m/z (%) = 240 (M+, 94), 213 (15), 212 (96), 184 (15), 183 (100), 182 (12), 181 (10), 163 (11), 157 (13), 91 (10). HRMS (EI): Calcd. for [[M + H]+: C15H9FO2]+: 241.06593, found: 241.06566.
6-Chloro-3-phenyl-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.73 (t, J = 0.5 Hz, 1H), 7.72–7.66 (m, 2H), 7.53 (d, J = 2.4 Hz, 1H), 7.50–7.41 (m, 4H), 7.31 (dt, J = 8.8, 0.6 Hz, 1H). 13C-NMR (75 MHz, Chloroform-d) δ 160.02, 151.88, 138.45, 134.25, 131.31, 129.75, 128.69–128.43 (m), 129.56, 129.25, 128.58, 127.10, 120.73, 117.93. GC-MS (EI, 70 ev): m/z (%) = 256 (M+, 100), 230 (30), 229 (15), 166 (10), 165 (77), 164 (20), 163 (28), 139 (18), 82 (18), 63 (15).
Methyl-2-oxo-3-phenyl-2H-chromene-6-carboxylate: 7t1H-NMR (300 MHz, Chloroform-d) δ 8.28 (d, J = 2.0 Hz, 1H), 8.19 (dd, J = 8.7, 2.0 Hz, 1H), 7.89–7.84 (m, 1H), 7.76–7.65 (m, 2H), 7.55–7.34 (m, 5H), 3.96 (s, 3H). 13C-NMR (75 MHz, Chloroform-d) δ 165.70, 159.85, 156.21, 139.23, 134.17, 132.28, 129.94, 129.19, 128.56, 128.50, 128.35, 126.59, 119.39, 116.65, 52.47. GC-MS (EI, 70 ev): m/z (%) = 280 (M+, 100), 252 (11), 249 (30), 221 (45), 193 (29), 165 (27), 164 (12), 163 (14), 139 (22), 83 (15).
8-Methyl-3-phenyl-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.79 (s, 1H), 7.75–7.64 (m, 2H), 7.51–7.27 (m, 5H), 7.19 (dd, J = 8.1, 7.0 Hz, 1H), 2.49 (s, 3H). 13C-NMR (75 MHz, Chloroform-d) δ 160.59, 151.78, 140.19, 134.76, 132.61, 129.02, 128.64, 128.43, 128.35, 127.80, 125.78, 125.56, 123.97, 119.29, 15.38. GC-MS (EI, 70 ev): m/z (%) = 236 (M+, 100), 209 (12), 208 (76), 207 (45), 179 (19), 178 (36), 165 (30), 152 (12), 89 (14), 77 (10), 76 (12).
6,8-Dichloro-3-phenyl-2H-chromen-2-one: 7v1H-NMR (300 MHz, Chloroform-d) δ 7.75–7.63 (m, 3H), 7.57 (d, J = 2.3 Hz, 1H), 7.48–7.39 (m, 4H). 13C-NMR (75 MHz, Chloroform-d) δ 158.81, 147.77, 137.89, 133.72, 131.20, 130.23, 129.50, 129.48, 128.60, 128.51, 125.61, 122.27, 121.44. GC-MS (EI, 70 ev): m/z (%) = 291 (M+, 63), 290 (94), 266 (11), 265 (10), 264 (65), 263 (16), 262 (100), 201 (20), 200 (10), 199 (62), 164 (28), 163 (60), 162 (10), 139 (10), 99 (16), 87 (11), 81 (19), 63 (10).
7-Chloro-3-phenyl-2H-chromen-2-one: 1H-NMR (300 MHz, Chloroform-d) δ 7.66 (s, 1H), 7.61–7.52 (m, 2H), 7.44–7.30 (m, 4H), 7.28–7.24 (m, 1H), 7.21–7.09 (m, 1H). 13C-NMR (75 MHz, Chloroform-d) δ 159.84, 153.66, 138.90, 137.23, 134.30, 129.03, 128.64, 128.49, 128.44, 128.26, 125.08, 124.91, 118.21, 116.73. GC-MS (EI, 70 ev): m/z (%) = 256 (M+, 100), 230 (16), 228 (100), 166 (12), 165 (85), 164 (27), 163 (28), 139 (16), 115 (14), 114 (12), 82 (11), 63 (15). HRMS (EI): Calcd. for [[M + H]+: C15H9ClO2]+: 257.03638, found: 257.03614.
2-Phenyl-3H-benzo[f]chromen-3-one: 7u1H-NMR (300 MHz, Chloroform-d) δ 8.36 (d, J = 1.7 Hz, 1H), 8.09 (d, J = 8.4 Hz, 1H), 7.83–7.68 (m, 2H), 7.67–7.59 (m, 2H), 7.50 (ddd, J = 8.4, 7.0, 1.4 Hz, 1H), 7.42–7.26 (m, 5H). 13C-NMR (75 MHz, Chloroform-d) δ 160.55, 153.04, 135.60, 135.00, 132.62, 130.23, 129.01, 128.80, 128.50 (d, J = 2.1 Hz), 128.12, 127.10, 125.96, 121.34, 116.58, 113.65. GC-MS (EI, 70 ev): m/z (%) = 272 (M+, 92), 245 (23), 244 (100), 243 (23), 215 (60), 213 (27), 189 (10), 122 (10), 107 (25), 94 (18).
3-(o-Tolyl)-2H-chromen-2-one: 7x1H-NMR (300 MHz, Chloroform-d) δ 7.65 (s, 1H), 7.60–7.46 (m, 2H), 7.39 (ddt, J = 8.2, 1.2, 0.6 Hz, 1H), 7.36–7.28 (m, 3H), 7.28–7.22 (m, 2H). 13C-NMR (75 MHz, Chloroform-d) δ 160.21, 153.80, 141.59, 136.82, 134.66, 131.41, 130.30, 129.73, 128.81, 127.81, 125.85, 124.43, 119.28, 116.55, 19.92. GC-MS (EI, 70 ev): m/z (%) = 236 (M+, 100), 220 (12), 219 (64), 208 (37), 207 (86), 189 (27), 179 (26), 178 (53), 177 (10), 176 (11), 165 (24), 152 (21), 117 (12), 115 (23), 89 (18), 76 (14), 63 (18), 39 (11).
3-(m-Tolyl)-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.76 (s, 1H), 7.55–7.43 (m, 4H), 7.37–7.22 (m, 3H), 7.22–7.16 (m, 1H), 2.39 (s, 3H). 13C-NMR (75 MHz, Chloroform-d) δ 160.55, 153.42, 139.70, 138.03, 134.59, 131.24, 129.59, 129.09, 128.44, 128.32, 127.81, 125.60, 124.40, 119.65, 116.36, 21.45. GC-MS (EI, 70 ev): m/z (%) = 236 (M+, 100), 209 (14), 208 (81), 207 (18), 179 (14), 178 (30), 165 (38), 152 (13), 117 (11), 89 (13), 63 (10).
3-(p-Tolyl)-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.67 (s, 1H), 7.55–7.47 (m, 2H), 7.45–7.35 (m, 2H), 7.25 (dt, J = 7.8, 0.9 Hz, 1H), 7.21–7.09 (m, 3H), 2.29 (s, 3H). 13C-NMR (75 MHz, Chloroform-d) δ 160.60, 153.32, 139.12, 138.82, 131.71, 131.10, 129.09, 128.31, 128.17, 127.74, 124.36, 119.68, 116.30, 21.23. GC-MS (EI, 70 ev): m/z (%) = 236 (M+, 100), 209 (10), 208 (62), 207 (37), 179 (13), 178 (28), 165 (26), 152 (12), 89 (11), 63 (10), 114 (12), 82 (11), 63 (15).
3-(Naphthalen-1-yl)-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.97–7.87 (m, 2H), 7.84–7.76 (m, 2H), 7.64–7.41 (m, 7H), 7.38–7.30 (m, 1H). 13C-NMR (75 MHz, Chloroform-d) δ 160.77, 153.97, 142.77, 133.66, 132.64, 131.65, 131.53, 129.36, 128.53, 128.37, 127.93, 127.63, 126.48, 126.07, 125.23, 124.54, 119.32, 116.68. GC-MS (EI, 70 ev): m/z (%) = 272 (M+, 100), 273 (19), 271 (79), 255 (11), 244 (24), 243 (50), 216 (11), 215 (58), 214 (10), 213 (28), 189 (17), 107 (18), 95 (17), 63 (11).
3-(4-Methoxyphenyl)-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.75 (s, 1H), 7.71–7.63 (m, 2H), 7.56–7.44 (m, 2H), 7.34 (ddd, J = 8.0, 1.3, 0.7 Hz, 1H), 7.31–7.23 (m, 1H), 7.02–6.90 (m, 2H), 3.85 (s, 3H). 13C-NMR (75 MHz, Chloroform-d) δ 160.74, 160.10, 153.24, 138.43, 130.95, 129.78, 127.81, 127.65, 127.02, 124.38, 119.79, 116.32, 113.87, 55.32. GC-MS (EI, 70 ev): m/z (%) = 252 (M+, 100), 224 (10), 210 (10), 209 (65), 181 (41), 152 (35).
3-(3-Methoxyphenyl)-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.81 (s, 1H), 7.53 (td, J = 7.4, 1.6 Hz, 2H), 7.40–7.32 (m, 2H), 7.32–7.25 (m, 3H), 6.95 (ddd, J = 8.1, 2.6, 1.2 Hz, 1H), 3.85 (s, 3H). 13C-NMR (75 MHz, Chloroform-d) δ 160.41, 159.48, 153.45, 139.94, 135.96, 131.40, 129.43, 128.09, 127.89, 124.44, 120.86, 119.55, 116.38, 114.47, 114.16, 55.32. GC-MS (EI, 70 ev): m/z (%) = 252 (M+, 100), 224 (46), 194 (10), 182 (10), 181 (68), 167 (10), 165 (21), 153 (13), 152 (62), 151 (16), 127 (10), 126 (14), 63 (16), 39 (10).
3-(4-Fluorophenyl)-2H-chromen-2-one: 7u1H-NMR (300 MHz, Chloroform-d) δ 7.79 (s, 1H), 7.75–7.64 (m, 2H), 7.54 (ddt, J = 7.6, 6.0, 1.8 Hz, 2H), 7.37 (dt, J = 8.8, 0.8 Hz, 1H), 7.34–7.27 (m, 1H), 7.19–7.06 (m, 2H). 13C-NMR (75 MHz, Chloroform-d) δ 164.70, 160.51, 153.47, 139.65, 131.48, 130.70, 130.39 (d, J = 8.3 Hz), 127.87, 127.30, 124.56, 119.54, 116.47, 115.46 (d, J = 21.6 Hz). GC-MS (EI, 70 ev): m/z (%) = 240 (M+, 93), 212 (100), 184 (14), 183 (81), 181 (14), 157 (19), 107 (12), 106 (21), 92 (12), 91 (13).
3-(3-Fluorophenyl)-2H-chromen-2-one: 7y1H-NMR (300 MHz, Chloroform-d) δ 7.79 (s, 1H), 7.56–7.47 (m, 2H), 7.47–7.38 (m, 2H), 7.38–7.28 (m, 2H), 7.27–7.19 (m, 1H), 7.05 (tdd, J = 8.3, 2.6, 1.1 Hz, 1H). 13C-NMR (75 MHz, Chloroform-d) δ 164.24, 160.57 (d, J = 61.2 Hz), 153.54, 140.38, 136.63 (d, J = 8.1 Hz), 131.78, 129.95 (d, J = 8.4 Hz), 128.04, 126.99 (d, J = 2.4 Hz), 124.61, 124.13 (d, J = 3.1 Hz), 119.36, 116.49, 115.84 (d, J = 7.0 Hz), 115.55 (d, J = 8.9 Hz). GC-MS (EI, 70 ev): m/z (%) = 240 (M+, 80), 212 (90), 183 (100), 157 (10), 63 (10).
Dibenzo[b,f]oxepine-10-carbonitrile: 91H-NMR (300 MHz, Chloroform-d) δ 7.62 (dd, J = 8.1, 1.7 Hz, 1H), 7.54–7.41 (m, 3H), 7.35–7.18 (m, 5H). 13C-NMR (75 MHz, Chloroform-d) δ 158.30, 157.43, 142.37, 132.86, 131.91, 130.42, 128.29, 128.03, 126.17, 125.60, 125.41, 121.91, 121.67, 118.46, 113.99.GC-MS (EI, 70 ev): m/z (%) = 219 (M+, 100), 191 (25), 190 (93), 165 (12), 164 (30), 163 (25), 82 (10), 63 (12).
3-(3-Chlorophenyl)-2H-chromen-2-one: 1H-NMR (300 MHz, Chloroform-d) δ 7.83 (s, 1H), 7.70 (td, J = 1.7, 1.0 Hz, 1H), 7.64–7.59 (m, 1H), 7.59–7.51 (m, 2H), 7.42–7.37 (m, 2H), 7.37–7.28 (m, 2H). 13C-NMR (75 MHz, Chloroform-d) δ 160.15, 153.59, 140.43, 136.35, 134.38, 131.82, 129.68, 128.89, 128.54, 128.05, 126.96, 126.74, 124.63, 119.37, 116.53. GC-MS (EI, 70 ev): m/z (%) = 256 (M+, 100), 230 (27), 229 (17), 228 (95), 166 (10), 165 (80), 164 (22), 163 (27), 139 (12), 110 (10), 82 (13), 75 (12), 63 (12). HRMS (EI): Calcd. for [[M + H]+: C15H9ClO2]+: 257.03638, found: 257.03614.
3-(4-Chlorophenyl)-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.82 (d, J = 0.6 Hz, 1H), 7.71–7.62 (m, 2H), 7.59–7.50 (m, 2H), 7.46–7.40 (m, 2H), 7.37 (dt, J = 8.9, 0.8 Hz, 1H), 7.34–7.28 (m, 1H). 13C-NMR (75 MHz, Chloroform-d) δ 160.32, 153.52, 139.91, 134.92, 133.05, 131.66, 129.82, 128.67, 127.95, 127.15, 124.60, 119.46, 116.50. GC-MS (EI, 70 ev): m/z (%) = 256 (M+, 100), 230 (24), 229 (10), 228 (73), 165 (60), 164 (18), 163 (20).
3-(Pyridin-3-yl)-2H-chromen-2-one: 7z1H-NMR (300 MHz, Chloroform-d) δ 8.80 (d, J = 2.4 Hz, 1H), 8.61 (dd, J = 4.9, 1.7 Hz, 1H), 8.05 (d, J = 8.5 Hz, 1H), 7.28–7.22 (m, 1H), 7.44–7.31 (m, 3H), 7.25 (s, 1H), 7.14 (td, J = 7.6, 1.0 Hz, 2H). 13C-NMR (75 MHz, Chloroform-d) δ 153.33, 149.55, 149.14, 136.43, 134.27, 132.25, 130.90, 127.68, 123.61, 122.92, 119.62, 115.38. GC-MS (EI, 70 ev): m/z (%) = 221 (M+, 100), 222 (26), 139 (12).
4-Methyl-3-phenyl-2H-chromen-2-one: 7t1H-NMR (300 MHz, Chloroform-d) δ 7.69 (dd, J = 8.0, 1.5 Hz, 1H), 7.55 (ddd, J = 8.6, 7.2, 1.5 Hz, 1H), 7.50–7.36 (m, 4H), 7.36–7.28 (m, 3H), 2.32 (s, 3H). 13C-NMR (75 MHz, Chloroform-d) δ 160.93, 152.66, 147.59, 134.42, 131.29, 129.99, 128.40, 128.18, 127.33, 125.08, 124.22, 120.54, 116.85, 16.56. GC-MS (EI, 70 ev): m/z (%) = 236 (M+, 96), 235 (82), 208 (60), 207 (100), 179 (24), 178 (62), 177 (11), 176 (13), 165 (22), 152 (22), 151 (10), 139 (15), 131 (28), 115 (20), 102 (12), 89 (23), 77 (21), 75 (10), 63 (21), 51 (17), 50 (10), 39 (15).
3,4-Diphenyl-2H-chromen-2-one: 101H-NMR (300 MHz, Chloroform-d) δ 7.54 (ddd, J = 8.6, 6.6, 2.2 Hz, 1H), 7.44 (ddd, J = 8.3, 1.2, 0.6 Hz, 1H), 7.34–7.28 (m, 3H), 7.23–7.10 (m, 9H). 13C-NMR (75 MHz, Chloroform-d) δ 161.26, 153.22, 151.57, 134.46, 133.84, 131.43, 130.51, 129.35, 128.33, 128.25, 127.78, 127.73, 127.63, 126.99, 124.11, 120.51, 116.76. GC-MS (EI, 70 ev): m/z (%) = 298 (M+, 100), 297 (90), 281 (11), 270 (28), 269 (28), 268 (16), 255 (13), 253 (17), 252 (11), 241 (32), 240 (10), 239 (47), 165 (12), 119 (19).
2H-Chromen-2-one: 7m1H-NMR (300 MHz, Chloroform-d) δ 7.62 (d, J = 9.6 Hz, 1H), 7.50–7.35 (m, 2H), 7.30–7.13 (m, 2H), 6.34 (d, J = 9.5 Hz, 1H). 13C-NMR (75 MHz, Chloroform-d) δ 160.74, 154.03, 143.39, 131.80, 127.83, 124.39, 118.81, 116.88, 116.69. GC-MS (EI, 70 ev): m/z (%) = 146 (M+, 56), 118 (100), 90 (44), 89 (41), 64 (10), 63 (28), 62 (12).
(Z)-2,3-Diphenylacrylonitrile: 111H-NMR (300 MHz, Chloroform-d) δ 7.98–7.85 (m, 2H), 7.73–7.64 (m, 2H), 7.55 (s, 1H), 7.52–7.39 (m, 6H). 13C-NMR (75 MHz, Chloroform-d) δ 142.20, 134.41, 133.66, 130.49, 129.22, 129.16, 129.02, 128.91, 125.95, 117.95, 111.64. GC-MS (EI, 70 ev): m/z (%) = 205 (M+, 100), 204 (92), 203 (26), 190 (52), 178 (23), 177 (27), 176 (24), 165 (13), 151 (13), 102 (12), 89 (14), 88 (11), 77 (11), 76 (16), 75 (11), 63 (13), 51 (22), 50 (14), 39 (11).
(Z)-3-(4-Hydroxyphenyl)-2-phenylacrylonitrile: 111H-NMR (300 MHz, DMSO-d6) δ 10.29 (s, 1H), 7.93–7.76 (m, 3H), 7.75–7.64 (m, 2H), 7.54–7.43 (m, 2H), 7.42–7.31 (m, 1H), 6.92 (d, J = 8.7 Hz, 2H). 13C-NMR (75 MHz, DMSO-d6) δ 160.02, 142.91, 134.37, 131.44, 129.14, 128.61, 125.41, 124.79, 118.64, 115.89, 105.85. GC-MS (EI, 70 ev): m/z (%) = 221 (M+, 100), 206 (18), 204 (10), 203 (11), 202 (24), 192 (11), 191 (14) 190 (19), 177 (11), 165 (40), 164 (13), 63 (12), 51 (16), 39 (10).