10.1071/CH17272_AC CSIRO 2017 Australian Journal of Chemistry 2017, 70(12), 1285-1290 SUPPLEMENTARY MATERIAL A Facile and Convenient Approach for the Synthesis of Novel Sesamol-Oxazine and Quinoline- Oxazine Hybrids Garima Khanna, A Pooja Saluja, A and Jitender M. Khurana A,B A Department of Chemistry, University of Delhi, Delhi-110007, India. B Corresponding author. Email: jmkhurana@chemistry.du.ac.in 1
Spectral data 7-(4-Chlorophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIa) Pale yellow solid; m.p. 369-371K (decompose); IR (νmax cm 1 ) (CHCl3): 2891, 1478, 1208, 1093; 1 H NMR (400 MHz, CDCl3) δ = 7.20-7.18 (m, 2H, ArH), 7.00-6.98 (m, 2H, ArH), 6.43 (s, 1H, ArH), 6.33 (s, 1H, ArH), 5.84 (s, 2H, CH2), 5.21 (s, 2H, CH2), 4.46 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 148.72, 147.00, 146.87, 141.85, 129.13, 126.48, 119.64, 111.66, 105.86, 100.86, 98.88, 79.31, 50.56; HRMS (ESI) calcd. for C15H12ClNO3 [M + H] + : 290.0584, found: 290.0589 [M + H] +. 7-(4-Methylphenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIb) Pale yellow solid; m.p. 372-374K (decompose); IR (νmax cm 1 ) (CHCl3): 2888, 1472, 1187, 1034; 1 H NMR (400 MHz, CDCl3) δ = 7.06-6.97 (m, 4H, ArH), 6.44 (s, 1H, ArH), 6.33 (s, 1H, ArH), 5.83(s, 2H, CH2), 5.23 (s, 2H, CH2), 4.46 (s, 2H, CH2), 2.25 (s, 3H, CH3); 13 C NMR (100 MHz, CDCl3) δ = 148.89, 146.71, 146.05, 141.65, 131.14, 129.76, 118.69, 112.10, 105.62, 100.76, 98.84, 79.98, 50.59, 20.52; HRMS (ESI) calcd. for C16H16NO3 [M + H] + : 270.1130, found: 270.1133 [M + H] +. 7-(4-Fluorophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIc) Pale yellow solid; m.p. 353-355K (decompose); IR (νmax cm 1 ) (CHCl3): 2894, 1472, 1209, 1037; 1 H NMR (400 MHz, CDCl3) δ = 7.05-7.02 (m, 2H, ArH), 6.96-6.90 (m, 2H, ArH), 6.43 (s, 1H, ArH), 6.34 (s, 1H, ArH), 5.84 (s, 2H, CH2), 5.19 (s, 2H, CH2), 4.44 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 158.14 (d, 1 JC-F = 239 Hz), 148.77, 146.83, 144.87, 141.80, 120.50 (d, 3 JC-F = 7.6 Hz), 115.71 (d, 2 JC-F = 22 Hz), 111.73, 105.55, 100.83, 98.85, 80.16, 51.02; HRMS (ESI) calcd. for C15H12FNO3 [M + H] + : 274.0879, found: 274.0877 [M + H] +. 7-(4-Methoxyphenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IId) Light yellow solid; m.p. 379-381K (decompose); IR (νmax cm 1 ) (CHCl3): 2897, 1509, 1478, 1215, 1038; 1 H NMR (400 MHz, CDCl3) δ = 7.03 (s, 2H, J = 8.4 Hz, ArH), 6.791 (d, 2H, J = 8.4 Hz, ArH), 6.43 (s, 1H, ArH), 6.34 (s, 1H, ArH), 5.84 (s, 2H, CH2), 5.18 (s, 2H, CH2), 4.42 (s, 2H, CH2), 3.73 (s, 3H, OCH3); 13 C NMR (100 MHz, CDCl3) δ = 155.01, 148.92, 146.75, 142.36, 141.68, 120.78, 114.49, 112.08, 105.62, 100.76, 98.84, 80.71, 55.48, 51.10; HRMS (ESI) calcd. for C16H15NO4 [M + H] + : 286.1079, found: 286.1083 [M + H] +. 7-(3-Chloro-4-fluorophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2- e][1,3]oxazine (IIe) 2
Light yellow solid; m.p. 371-373K (decompose); IR (νmax cm 1 ) (CHCl3): 2893, 1474, 1208, 1039; 1 H NMR (400 MHz, CDCl3) δ = 7.11-7.09 (m, 1H, ArH), 7.02-6.98 (m, 1H, ArH), 6.94-6.90 (m, 1H, ArH), 6.42 (s, 1H, ArH), 6.35 (s, 1H, ArH), 5.85 (s, 2H, CH2), 5.18 (s, 2H, CH2), 4.44 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 153.39 (d, 1 JC-F = 242 Hz), 148.64, 146.99, 145.48 (d, 4 JC-F = 2.8 Hz), 141.99, 120.74, 118.38 (d, 3 JC-F = 6.7 Hz), 116.75 (d, 2 JC-F = 22 Hz), 111.38, 105.51, 100.91, 98.95, 79.54, 50.98; HRMS (ESI) calcd. for C15H11ClFNO3 [M+ H] + : 308.0490, found: 308.0485 [M + H] +, 310.0504 [M + H + 2] +. 7-(3-Cyanophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIf) Light yellow solid; m.p. 410-412K (decompose); IR (νmax cm 1 ) (CHCl3): 2900, 2224, 1480, 1218, 1055; 1 H NMR (400 MHz, CDCl3) δ = 7.34-7.19 (m, 4H, ArH), 6.47 (s, 1H, ArH), 6.37 (s, 1H, ArH), 5.87 (s, 2H, CH2), 5.27 (s, 2H, CH2), 4.53 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 148.86, 148.62, 147.08, 142.13, 130.07, 124.64, 122.64, 120.95, 118.91, 113.16, 111.24, 105.48, 100.97, 98.97, 78.45, 50.31; HRMS (ESI) calcd. for C16H12N2O3 [M + H] + : 281.0924, found: 281.0930 [M + H] +. 7-(4-Bromophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIg) Light yellow solid; m.p. 379-381K (decompose); IR (νmax cm 1 ) (CHCl3): 2892, 1483, 1212, 1047; 1 H NMR (400 MHz, CDCl3) δ = 7.32 (d, 2H, J = 8.4Hz, ArH), 6.94 (d, 2H, J = 9.2 Hz, ArH), 6.43 (s, 1H, ArH), 6.33 (s, 1H, ArH), 5.84 (s, 2H, CH2), 5.22 (s, 2H, CH2), 4.46 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 148.74, 147.48, 146.91, 141.89, 132.08, 120.01, 113.90, 111.66, 105.55, 100.88, 98.90, 79.19, 50.51; HRMS (ESI) calcd. for C15H12BrNO3 [M + H] + : 334.0079, found: 334.0073 [M + H] +, 336.0054 [M + H + 2] + 7-(3,4-Dichlorophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIh) Light yellow solid; m.p. 395-397K (decompose); IR (νmax cm 1 ) (CHCl3): 2892, 1474, 1211, 1044; 1 H NMR (400 MHz, CDCl3) δ = 7.20 (d, 1H, J = 9.2 Hz, ArH), 7.07 (s, 1H, ArH), 6.83 (d, 1H, J = 6.8 Hz), 6.37(s, 1H, ArH), 6.28 (s, 1H, ArH), 5.79 (s, 2H, CH2), 5.13 (s, 2H, CH2), 4.39 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 148.61, 147.90, 147.01, 142.04, 132.86, 130.63, 124.36, 119.72, 117.54, 111.36, 105.49, 100.94, 98.96, 78.69, 50.46; HRMS (ESI) calcd. for C15H11Cl2NO3 [M + H] + : 324.0194, found: 324.0183 [M + H] +, 326.0157 [M + H + 2] +, 328.0150 [M + H + 4] +. 7-(4-Iodophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIi) 3
Pale yellow solid; m.p. 368-370K (decompose); IR (νmax cm 1 ) (CHCl3): 2890, 1480, 1212, 1044; 1 H NMR (400 MHz, CDCl3) δ = 7.51 (d, 2H, J = 8.4 Hz, ArH), 6.83 (d, 2H, J = 8.4 Hz, ArH), 6.43 (s, 1H, ArH), 6.33 (s, 1H, ArH), 5.84 (s, 2H, CH2), 5.21 (s, 2H, CH2), 4.46 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 148.73, 148.10, 146.91, 141.89, 138.01, 120.32, 111.67, 105.55, 100.88, 98.91, 83.85, 78.97, 50.36; HRMS (ESI) calcd. for C15H12INO3 [M + H] + : 381.9940, found: 381.9935 [M + H] +. 7-(3-Nitrophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIj) Yellow solid; m.p. 389-391K (decompose); IR (νmax cm 1 ) (CHCl3): 2895, 1526, 1478, 1212, 1044; 1 H NMR (400 MHz, CDCl3) δ = 7.88 (s, 1H, ArH), 7.74-7.72 (m, 1H, ArH), 7.40-7.34 (m, 2H, ArH), 6.47 (s, 1H, ArH), 6.36 (s, 1H, ArH), 5.85 (s, 2H, CH2), 5.30 (s, 2H, CH2), 4.57 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 149.24, 149.16, 148.65, 147.12, 142.20, 129.97, 123.30, 115.75, 112.25, 111.26, 105.52, 101.01, 99.02, 78.32, 50.74; HRMS (ESI) calcd. for C15H12N2O5 [M + H] + : 301.0824, found: 301.0818 [M + H] +. Methyl 4-(6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazin-7(8H)-yl)benzoate (IIk) Light yellow solid; m.p. 411-413K (decompose); IR (νmax cm 1 ) (CHCl3): 2880, 1698, 1479, 1185, 1059; 1 H NMR (400 MHz, CDCl3) δ = 7.88-7.86 (m, 2H, ArH), 6.98-6.96 (m, 2H, ArH), 6.41 (s, 1H, ArH), 6.31 (s, 1H, ArH), 5.80 (s, 2H, CH2), 5.24 (s, 2H, CH2), 4.50 (s, 2H, CH2), 3.79 (s, 3H, COOMe); 13 C NMR (100 MHz, CDCl3) δ = 166.85, 151.68, 148.82, 146.97, 142.12, 131.26, 121.26, 115.75, 111.78, 105.53, 100.97, 99.01, 77.73, 51.79, 49.56; HRMS (ESI) calcd. for C17H15NO5 [M + H] + : 314.1028, found: 314.1028 [M + H] +. 7-(4-Nitrophenyl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':4,5]benzo[1,2-e][1,3]oxazine (IIl) Yellow solid; m.p. 439-441K (decompose); IR (νmax cm 1 ) (CHCl3): 1598, 1485, 1212, 1060; 1 H NMR (400 MHz, DMSO-d6) δ = 8.07 (d, 2H, J = 8.4 Hz, ArH), 7.20 (d, 2H, J = 8.4 Hz, ArH), 6.69 (s, 1H, ArH), 6.43 (s, 1H, ArH), 5.88 (s, 2H, CH2), 5.45 (s, 2H, CH2), 4.65 (s, 2H, CH2); 13 C NMR (100 MHz, DMSO-d6) δ = 152.82, 148.22, 146.58, 141.68, 138.99, 125.66, 114.80, 112.27, 106.22, 100.98, 98.50, 76.47, 47.79; HRMS (ESI) calcd. for C15H12N2O5 [M + H] + : 301.0824, found: 301.0821 [M + H] +. 2-(4-Chlorophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIa) Light yellow solid; m.p. 410-412K (decompose); IR (νmax cm 1 ) (CHCl3): 2840, 1591, 1217, 1039; 1 H NMR (400 MHz, CDCl3) δ = 8.80-8.79 (m, 1H, ArH), 8.01 (d, 1H, J = 8.4 Hz, ArH), 7.90 (d, 1H, J = 9.2 Hz, ArH), 7.41-7.38 (m, 1H), 7.26-7.18 (m, 3H, ArH), 7.08-7.04 (m, 2H, ArH), 5.39 (s, 2h, CH2), 4.90 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 152.33, 147.83, 4
147.14, 144.36, 129.91, 129.29, 129.11, 127.07, 126.18, 122.38, 121.33, 120.04, 111.83, 79.60, 48.06; HRMS (ESI) calcd. for C17H13ClN2O [M + H] + : 297.0789, found: 297.0789 [M + H] +, 299.0767 [M + H + 2] +. 2-(4-Methylphenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIb) Pale yellow solid; m.p. 379-381K (decompose); IR (νmax cm 1 ) (CHCl3): 1506, 1226, 1099; 1 H NMR (400 MHz, CDCl3) δ = 8.78-8.77 (m, 1H, ArH), 8.01 (d, 1H, J = 8.4 Hz, ArH), 7.89 (d, 1H, J = 9.2 Hz, ArH), 7.40-7.37(m, 1H, ArH), 7.26-7.25 (m, 1H, ArH), 7.05-7.03 (m, 4H, ArH), 5.40 (s, 2H, CH2), 4.89 (s, 2H, CH2), 2.25 (s, 3H, CH3); 13 C NMR (100 MHz, CDCl3) δ = 152.35, 147.63, 146.10, 144.25, 131.60, 129.82, 129.56, 129.18, 126.20, 122.40, 121.18, 118.96, 112.12, 80.15, 47.96, 20.51; HRMS (ESI) calcd. for C18H16N2O [M + H] + : 277.1333, found: 277.1320 [M + H] +. 2-(4-Fluorophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIc) Pale yellow solid; m.p. 403-405K (decompose); IR (νmax cm 1 ) (CHCl3): 2891, 1503, 1223, 1046; 1 H NMR (400 MHz, CDCl3) δ = 8.76 (s, 1H, ArH), 7.98-7.89 (m, 2H, ArH), 7.37-6.91 (m, 6H, ArH), 5.33 (s, 2H, CH2), 4.84 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 158.33 (d, 1 JC-F = 241 Hz), 152.28, 147.73, 144.93, 144.29, 129.71, 129.15, 126.14, 122.37, 121.26, 120.84 (d, 3 JC-F = 7.6 Hz), 115.82 (d, 2 JC-F = 22 Hz), 111.85, 80.34, 48.40; HRMS (ESI) calcd. for C17H13FN2O [M + H] + : 281.1090, found: 281.1086 [M + H] +. 2-(4-Methoxyphenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIId) Pale green solid; m.p. 369-371K (decompose); IR (νmax cm 1 ) (CHCl3): 2835, 1505, 1234, 1032; 1 H NMR (400 MHz, CDCl3) δ = 8.74-8.73 (m, 1H, ArH), 8.25-8.17 (m, 2H, ArH), 7.56-7.54 (m, 1H, ArH), 7.32 (d, 1H, J = 9.2 Hz, ArH), 7.03-7.01 (m, 2H, ArH), 6.74-6.72 (m, 2H, ArH), 5.33 (s, 2H, CH2), 4.83 (s, 2H, CH2), 3.66 (s, 3H, OCH3); 155.46, 153.81, 143.44, 141.84, 139.34, 133.69, 126.90, 125.80, 125.20, 121.24, 121,14, 114.55, 112.69, 81.11, 55.43, 48.43; HRMS (ESI) calcd. for C18H16N2O2 [M + H] + : 293.1285, found: 293.1281 [M + H] +. 2-(3-Chloro-4-fluorophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIe) Light yellow solid; m.p. 389-391K (decompose); IR (νmax cm 1 ) (CHCl3): 1497, 1224, 1048; 1 H NMR (400 MHz, CDCl3) δ = 8.79-8.77 (m, 1H, ArH), 7.98 (d, 1H, J = 8.4 Hz, ArH), 7.90 (d, 1H, J = 9.2 Hz, ArH), 7.40-7.37 (m, 1H, ArH), 7.26-7.24 (m, 1H, ArH), 7.17-7.15 (m, 1H, ArH), 6.99-6.97 (m, 2H, ArH), 5.33 (s, 2H, CH2), 4.86 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 153.59 (d, 1 JC-F = 242 Hz), 152.14, 147.92, 145.51 (d, 4 JC-F = 3 Hz), 144.37, 129.96, 129.10, 126.06, 122.35, 121.36, 121.09, 118.62 (d, 3 JC-F = 6.7 Hz), 116.85 (d, 2 JC-F = 22 Hz), 5
111.58, 79.64, 48.49; HRMS (ESI) calcd. for C17H12ClFN2O [M + H] + : 315.0700, found: 315.0695 [M + H] +, 317.0670 [M + H + 2] + 2-(3-Cyanophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIf) Light yellow solid; m.p. 411-413K (decompose); IR (νmax cm 1 ) (CHCl3): 2853, 2229, 1601, 1485, 1234, 1047; 1 H NMR (400 MHz, CDCl3) δ = 8.76-8.75 (m, 1H, ArH), 7.98 (d, 1H, J = 8.4 Hz, ArH), 7.87 (d, 1H, J = 8.8 Hz, ArH), 7.39-7.29 (m, 4H, ArH), 7.23-7.14 (m, 2H, ArH), 5.37 (s, 2H, CH2), 4.89 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 152.21, 148.91, 147.87, 144.18, 130.23, 129.90, 129.26, 126.07, 125.08, 122.58, 122.42, 121.51, 121.32, 118.77, 113.30, 111.52, 78.57, 47.99; HRMS (ESI) calcd. for C18H13N3O [M + H] + : 288.1119, found: 288.1102 [M + H] +. 2-(4-Bromophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIg) Light yellow solid; m.p. 401-403K (decompose); IR (νmax cm 1 ) (CHCl3): 2853, 1587, 1493, 1216, 1043; 1 H NMR (400 MHz, CDCl3) δ = 8.80-8.79 (m, 1H, ArH), 8.01 (d, 1H, J = 8.4 Hz, ArH), 7.90 (d, 1H, J = 8.4 Hz, ArH), 7.41-7.33 (m, 3H, ArH), 7.26-7.22 (m, 1H, ArH), 7.01 (d, 2H, J = 8.4 Hz, ArH), 5.38 (s, 2H,CH2), 4.89 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 152.24, 147.83, 147.52, 144.32, 132.17, 129.86, 129.09, 126.11, 122.33, 121.32, 120.30, 114.36, 111.79, 79.38, 47.94; HRMS (ESI) calcd. for C17H13BrN2O [M + H] + : 341.0290, found: 341.0281 [M + H] +, 343.0265 [M + H + 2] +. 2-(3,4-Dichlorophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIh) Light yellow solid; m.p. 387-389K (decompose); IR (νmax cm 1 ) (CHCl3): 2895, 1591, 1229, 1011; 1 H NMR (400 MHz, CDCl3) δ = 8.80-8.79 (m, 1H, ArH), 8.02 (d, 1H, J = 8.4 Hz, ArH), 7.92 (d, 1H, J = 9.2 Hz, ArH), 7.43-7.40 (m, 1H, ArH), 7.27-7.24 (m, 2H, ArH), 7.20-7.19 (m, 1H, ArH), 6.96-6.93 (m, 1H, ArH), 5.36 (s, 2H, CH2), 4.88 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 152.25, 147.91, 147.59, 143.90, 133.01, 130.76, 129.50, 126.13, 124.94, 122.56, 121.47, 120.12, 117.81, 111.64, 78.88, 48.05; HRMS (ESI) calcd. for C17H12Cl2N2O [M + H] + : 331.0405, found: 331.0399 [M + H] +, 333.0371 [M + H + 2] +, 335.0346 [M + H + 4] + 2-(3-Nitrophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIi) Yellow solid; m.p. 413-415K (decompose); IR (νmax cm 1 ) (CHCl3): 1526, 1231, 1045; 1 H NMR (400 MHz, CDCl3) δ = 8.81-8.80 (m, 1H, ArH), 8.07 (d, 1H, J = 8.4 Hz, ArH), 7.96-7.92 (m, 2H, ArH), 7.75 (d, 1H, J = 7.6 Hz, ArH), 7.46-7.37 (m, 3H, ArH), 7.28-7.24 (m, 1H, ArH), 5.46 (s, 2H, CH2), 4.99 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 152.28, 149.22, 149.14, 147.66, 143.87, 130.12, 129.58, 129.56, 126.12, 123.45, 122.57, 121.56, 116.16, 112.60, 6
111.59, 78.38, 48.07; HRMS (ESI) calcd. for C17H13N3O3 [M + H] + : 308.1035, found: 308.1030 [M + H] +. 2-(4-Iodophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIj) Yellow solid; m.p. 425-427K (decompose); IR (νmax cm 1 ) (CHCl3): 2851, 1585, 1228, 1045; 1 H NMR (400 MHz, CDCl3) δ = 8.80 (m, 1H, ArH), 8.02 (d, 1H, J = 8.4 Hz, ArH), 7.91 (d, 1H, J = 8.8 Hz), 7.54-7.51 (m, 1H, ArH), 7.42-7.39 (m, 1H, ArH), 7.26-7.25 (m, 1H, ArH), 6.92-6.89 (m, 1H, ArH), 5.39 (s, 2H, CH2), 4.90 (s, 2H, CH2); 13 C NMR (100 MHz, CDCl3) δ = 152.28, 148.15, 147.77, 138.13, 129.78, 129.20, 126.14, 122.40, 121.34, 120.61, 111.82, 84.40, 79.19, 47.83; HRMS (ESI) calcd. for C17H13IN2O [M + H] + : 389.0150, found: 389.0141 [M + H] +. Methyl 4-(1H-[1,3]oxazino[5,6-f]quinolin-2(3H)-yl)benzoate (IIIk) Pale yellow solid; m.p. 391-393K (decompose); IR (νmax cm 1 ) (CHCl3): 2884, 1707, 1609, 1268, 1052; 1 H NMR (400 MHz, CDCl3) δ = 8.75-8.74 (m, 1H, ArH), 8.01-7.85 (m, 4H, ArH), 7.38-7.35 (m, 1H, ArH), 7.23 (m, 1H, ArH), 7.06 (d, 2H, J = 9.2 Hz, ArH), 5.42 (s, 2H, CH2), 4.94 (s, 2H, CH2), 3.79 (s, 3H, CH3); 13 C NMR (100 MHz, CDCl3) δ = 166.75, 152.33, 151.71, 147.90, 144.27, 131.33, 129.87, 129.20, 122.41, 121.44, 116.17, 111.94, 77.97, 51.85, 47.24; HRMS (ESI) calcd. for C19H16N2O3 [M + H] + : 321.1236, found: 321.1230 [M + H] +. 2-(4-Nitrophenyl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIl) Yellow solid; m.p. 455-457K (decompose); IR (νmax cm 1 ) (CHCl3): 1596, 1505, 1271, 1043; 1 H NMR (400 MHz, DMSO-d6) δ = 8.77-8.75 (m, 1H, ArH), 8.38 (d, 1H, J = 8.4 Hz, ArH), 8.09 (d, 2H, J = 9.2 Hz, ArH), 7.81 (d, 1H, J = 9.2 Hz, ArH), 7.55-7.52 (m, 1H, ArH), 7.39-7.36 (m, 2H, ArH), 7.29 (d, 1H, J = 9.2 Hz, ArH), 5.65 (s, 2H, CH2), 5,13 (s, 2H, CH2); 13 C NMR (100 MHz, DMSO-d6) δ =152.78, 151.50, 148.28, 143.80, 139.13, 130.40, 129.45, 125.96, 125.65, 121.86, 121.74, 114.94, 113.21, 76.55, 45.81; HRMS (ESI) calcd. for C17H13N3O3 [M + H] + : 308.1035, found: 308.1031 [M + H] +. 2-(Pyridin-3-yl)-2,3-dihydro-1H-[1,3]oxazino[5,6-f]quinoline (IIIm, C 16 H 13 N 3 O) Light pink solid; m.p.: 397-399K (decompose); IR (νmax cm 1 ) (CHCl3): 2924, 1579, 1498, 1229, 1045; 1 H NMR (400 MHz, DMSO-d6) δ = 8.80-8.78 (m, 1H, ArH), 8.52 (d, 1H, J = 3.2 Hz, ArH), 8.12 (d, 1H, J = 4.4 Hz, ArH), 8.00 (d, 1H, J = 8.4 Hz, ArH), 7.90 (d, 1H, J = 9.2 Hz, ArH), 7.44-7.37 (m, 2H, ArH), 7.26-7.24 (m, 1H, ArH), 7.17-7.14 (m, 1H, ArH), 5.42 (s, 2H, CH2), 4.94 (s, 2H, CH2); 13 C NMR (100 MHz, DMSO-d6) δ =152.15, 147.94, 144.60, 7
144.36, 143.04, 141.29, 130.01, 129.06, 126.05, 125.39, 123.64, 122.31, 121.38, 111.53, 78.97, 47.87; HRMS (ESI) calcd. for C16H13N3O [M + H] + : 264.1137, found: 264.1132 [M + H] +. 8
Table S1: Crystal data and structure refinement for IIa Formula C 15 H 12 ClNO 3 Formula weight (g) 289.71 Temperature Wavelength 293(2) K 0.71073 Å Crystal system, space group Monoclinic, I 1 a 1 Unit cell dimensions a = 13.870 (7)Å alpha = 90 deg. b = 5.097 (2) Å c = 18.574 (10) Å Volume 1308.8 (11)Å 3 Z, Calculated density 4, 1.70 g/cm 3 Absorption coefficient 0.298 mm -1 F(000) 600 Crystal size Theta range for data collection Limiting indices 0.22 x 0.20 x 0.16 mm 3.3690 to 22.7170 deg. beta = 94.56 (5) deg. gamma = 90 deg. -18<=h<=17, -6<=k<=6, -24<=l<=25 Reflections collected / unique 3123 / 1407 [R(int) = 0.0608] Completeness to theta = 25.00 98 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00000 and 0.46452 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3123 / 0 / 182 Goodness-of-fit on F^2 0.943 Final R indices [I>2sigma(I)] R1 = 0.0537, wr2 = 0.0977 R indices (all data) R1 = 0.1513, wr2 = 0.1461 Largest diff. peak and hole 0.176 and -0.192 e.a -3 9
Table S2: Crystal data and structure refinement for IIIa Formula C 34 H 26 Cl 2 N 4 O 2 Formula weight (g) 593.49 Temperature 293(2) K Wavelength 0.71073 Å Crystal system, space group Triclinic, P -1 Unit cell dimensions a = 7.5024(6)Å α = 76.017(7) deg. b = 11.0561 (9) Å β = 83.449(7) deg. c = 17.5431 (15) Å γ = 78.000(7) deg. Volume 1378.00(2)Å 3 Z, Calculated density 2, 1.430 g/cm 3 Absorption coefficient 0.111 mm -1 F(000) 616 Crystal size 0.04 x 0.02 x 0.01 mm Theta range for data collection 2.95 to 29.482 deg. Limiting indices -10<=h<=10, -15<=k<=15, -24<=l<=2 Reflections collected / unique 6711 / 3195 [R(int) = 0.0631] Completeness to theta = 29.482 87.4 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00000 and 0.84961 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3195 / 0 / 379 Goodness-of-fit on F^2 1.005 Final R indices [I>2sigma(I)] R1 = 0.0577, wr2 = 0.1057 R indices (all data) R1 = 0.1411, wr2 = 0.1565 Largest diff. peak and hole 0.282 and -0.301 e.a -3 10
1 H NMR Spectrum of IIa 11
13 C NMR Spectrum of IIa 12
1 H NMR Spectrum of IIb 13
13 C NMR spectrum of IIb 14
1 H NMR spectrum of IIc 15
13 C NMR spectrum of IIc 16
1 H NMR spectrum of IId 17
13 C NMR spectrum of IId 18
1 H NMR spectrum of IIe 19
13 C NMR spectrum of IIe 20
1 H NMR spectrum of IIf 21
13 C NMR spectrum of IIf 22
1 H NMR spectrum of IIg 23
13 C NMR spectrum of IIg 24
1 H NMR spectrum of IIh 25
13 C NMR spectrum of IIh 26
1 H NMR spectrum of IIi 27
13 C NMR spectrum of IIi 28
1 H NMR spectrum of IIj 29
13 C NMR spectrum of IIj 30
1 H NMR spectrum of IIk 31
13 C NMR spectrum of IIk 32
1 H NMR spectrum of IIl 33
13 C NMR spectrum of IIl 34
1 H NMR spectrum of IIIa 35
13 C NMR spectrum of IIIa 36
1 H NMR spectrum of IIIb 37
13 C NMR spectrum of IIIb 38
1 H NMR spectrum of IIIc 39
13 C NMR spectrum of IIIc 40
1 H NMR spectrum of IIId 41
13 C NMR spectrum of IIId 42
1 H NMR spectrum of IIIe 43
13 C NMR spectrum of IIIe 44
1 H NMR spectrum of IIIf 45
13 C NMR spectrum of IIIf 46
1 H NMR spectrum of IIIg 47
13 C NMR spectrum of IIIg 48
1 H NMR spectrum of IIIh 49
13 C NMR spectrum of IIIh 50
1 H NMR spectrum of IIIi 51
13 C NMR spectrum of IIIi 52
1 H NMR spectrum of IIIj 53
13 C NMR spectrum of IIIj 54
1 H NMR spectrum of IIIk 55
13 C NMR spectrum of IIIk 56
1 H NMR spectrum of IIIl 57
13 C NMR spectrum of IIIl 58
1 H NMR spectrum of IIIm 59
13 C NMR spectrum of IIIm 60