5.3 Experimental Procedures and Analytical Data
5.3.1 Synthesis of N-Aryl-1,2,3-triazoles
Synthesis of 4-n-Butyl-1-(o-tolyl)-1H-1,2,3-triazole (123a):
The general procedure A was followed using 1-iodo-2-methylbenzene (1d) (4.36 g, 20 mmol), 1-hexyne (1.64 g, 20.0 mmol), NaN3 (1.36 g, 21.0 mmol), CuI (0.38 g, 2.0 mmol) and DMEDA (0.26 g, 3.0 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123a (2.94 g, 63%) as a colorless oil.
1H-NMR (300 MHz, CDCl3): δ = 7.46 (s, 1H), 7.43–7.27 (m, 4H), 2.90–2.73 (m, 2H), 2.20 (s, 3H), 1.83–1.63 (m, 2H), 1.54–1.35 (m, 2H), 0.96 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 148.3 (Cq), 136.9 (Cq), 133.8 (Cq), 131.5 (CH), 129.7 (CH), 126.9 (CH), 126.1 (CH), 122.4 (CH), 31.6 (CH2), 25.4 (CH2), 22.5 (CH2), 18.0 (CH3), 14.0 (CH3).
IR (ATR): 𝑣̃ = 2956, 2929, 2860, 1552, 1502, 1214, 1117, 1039, 988, 760 cm-1. MS (ESI) m/z (relative intensity): 238 (2) [M+Na+], 216 (100) [M+H+].
HR-MS (ESI) m/z calcd for C13H18N3, [M+H+] 216.1495, found 216.1507.
The spectral data are in accordance with those reported in the literature.15c
Synthesis of 4-n-Butyl-1-phenyl-1H-1,2,3-triazole (123b)
The general procedure A was followed using 1-iodo-benzene (1e) (2.01 g, 10.0 mmol), 1-hexyne (0.82 g, 10.0 mmol), NaN3 (0.68 g, 10.5 mmol), CuI (0.38 g, 1.0 mmol) and
DMEDA (0.26 g, 1.5 mmol). Purification by column chrommatography (n-pentane/EtOAc 5/1) yielded 123b (1.57 g, 78%) as a colorless solid.
M.r.: 58−59 °C.
The spectral data are in accordance with those reported in the literature.118
Synthesis of 4-n-Butyl-1-(m-tolyl)-1H-1,2,3-triazole (123c)
The general procedure A was followed using 1-iodo-3-methylbenzene (1f) (4.36 g, 20 mmol), 1-hexyne (1.64 g, 20.0 mmol), NaN3 (1.36 g, 21.0 mmol), CuI (0.38 g, 2.0 mmol) and DMEDA (0.26 g, 3.0 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123c (2.94 g, 63%) as an orange solid.
M.r.: 44−45 °C.
Synthesis of 4-n-Butyl-1-(3-methoxyphenyl)-1H-1,2,3-triazole (123d)
The general procedure A was followed using 1-iodo-3-methoxybenzene (1g) (2.18 g, 9.3 mmol), 1-hexyne (0.82 g, 10.0 mmol), NaN3 (0.68 g, 10.5 mmol), CuI (0.38 g, 1.0 mmol) and DMEDA (0.26 g, 1.5 mmol). Purification by column chrommatography (n-pentane/EtOAc 5/1) yielded 123d (2.00 g, 93%) as a colorless oil.
1H-NMR (300 MHz, CDCl3): δ = 7.70 (s, 1H), 7.36 (dd, J = 8.1, 8.1 Hz, 1H), 7.31 (dd, J = 2.3, 2.3 Hz, 1H), 7.24–7.18 (m, 1H), 6.91 (ddd, J = 8.3, 2.5, 0.9 Hz, 1H), 3.84 (s, 3H), 2.88–2.62 (m, 2H), 1.77–1.59 (m, 2H), 1.40 (ddt, J = 14.5, 9.3, 7.3 Hz, 2H), 0.93 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 160.6 (Cq), 149.2 (Cq), 138.4 (Cq), 130.5 (CH), 119.0 (CH), 114.3 (CH), 112.3 (CH), 106.3 (CH), 55.7 (CH3), 31.6 (CH2), 25.4 (CH2), 22.4 (CH2), 13.9 (CH3).
IR (ATR): 𝑣̃ = 2955, 2929, 2859, 1608, 1595, 1497, 1461, 1292, 1255, 1155 cm-1. MS (ESI) m/z (relative intensity): 270 (61) [M+K+], 254 (26) [M+Na+], 232 (100) [M+H+].
HR-MS (ESI) m/z calcd for C13H18N3O, [M+H+] 232.1444, found 232.1436.
Synthesis of 4-n-Butyl-1-(3-fluorophenyl)-1H-1,2,3-triazole (123e)
The general procedure A was followed using 1-fluoro-3-iodobenzene (1h) (4.40 g, 20.0 mmol), 1-hexyne (1.64 g, 20.0 mmol), NaN3 (1.36 g, 21.0 mmol), CuI (0.38 g, 2.0 mmol) and DMEDA (0.26 g, 3.0 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123e (3.77 g, 86%) as an orange solid.
M.p.: 41 °C.
1H-NMR (300 MHz, CDCl3): δ = 7.72 (s, 1H), 7.54–7.38 (m, 3H), 7.16–7.02 (m, 1H), 2.86– and DMEDA (0.26 g, 3.0 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123f (3.77 g, 86%) as a colorless oil.
1H-NMR (300 MHz, CDCl3): δ = 8.01–7.82 (m, 1H), 7.78 (dd, J = 3.0, 0.7 Hz, 1H), 7.46–7.30
Synthesis of 4-n-Butyl-1-(2-methoxyphenyl)-1H-1,2,3-triazole (123g)
The general procedure A was followed using 1-iodo-2-methoxybenzene (1j) (2.34 g, 10.0 mmol), 1-hexyne (0.82 g, 10.0 mmol), NaN3 (0.68 g, 10.5 mmol), CuI (0.38 g, 1.0 mmol) and DMEDA (0.26 g, 1.5 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123g (2.06 g, 89%) as a colorless oil.
1H-NMR (300 MHz, CDCl3): δ = 7.80 (s, 1H), 7.71 (dd, J = 8.3, 1.7 Hz, 1H), 7.35 (ddd, J = 8.4, 7.4, 1.7 Hz, 1H), 7.08−7.00 (m, 2H), 3.84 (s, 3H), 2.84–2.67 (m, 2H), 1.79–1.61 (m, 2H), 1.40 (dp, J = 9.4, 7.3 Hz, 2H), 0.93 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 151.2 (Cq), 147.7 (Cq), 129.8 (CH), 126.6 (Cq), 125.5 (CH), 122.9 (CH), 121.2 (CH), 112.3 (CH), 56.0 (CH3), 31.6 (CH2), 25.4 (CH2), 22.4 (CH2), 13.9 (CH3).
IR (ATR): 𝑣̃ = 2930, 2859, 1601, 1504, 1473, 1285, 1252, 1285, 1252, 1176 cm-1. MS (ESI) m/z (relative intensity): 254 (17) [M+Na+], 232 (100) [M+H+].
HR-MS (ESI) m/z calcd for C13H18N3O, [M+H+] 232.1444, found 232.1444.
The spectral data are in accordance with those reported in the literature.15c
Synthesis of 4-n-Butyl-1-(naphthalen-1-yl)-1H-1,2,3-triazole (123h)
The general procedure A was followed using 1-iodonaphthalene (1k) (5.08 g, 20.0 mmol), 1-hexyne (1.64 g, 20.0 mmol), NaN3 (1.36 g, 21.0 mmol), CuI (0.38 g, 2.0 mmol) and DMEDA (0.26 g, 3.0 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123h (4.03 g, 80%) as an orange oil.
1H-NMR (300 MHz, CDCl3): δ = 7.99–7.84 (m, 2H), 7.68–7.57 (m, 2H), 7.57–7.45 (m, 4H), 2.95–2.81 (m, 2H), 1.87–1.69 (m, 2H), 1.55–1.38 (m, 2H), 0.98 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 148.4 (Cq), 134.2 (Cq), 134.0 (Cq) 130.1 (CH), 128.7 (Cq), 128.3 (CH), 127.8 (CH), 127.0 (CH), 125.0 (CH), 123.5 (CH), 123.4 (CH), 122.5 (CH), 31.6 (CH2), 25.4 (CH2), 22.5 (CH2), 13.7 (CH3).
IR (ATR): 𝑣̃ = 3056, 2929, 2858, 1597, 1512, 1470, 1429, 1219, 1038, 800, 771, 434 cm-1. MS (ESI) m/z (relative intensity): 290 (87) [M+K+], 274 (28) [M+Na+], 252 (100) [M+H+].
HR-MS (ESI) m/z calcd for C16H18N3, [M+H+] 252.1495, found 252.1484.
Synthesis of 4-n-Butyl-1-(p-tolyl)-1H-1,2,3-triazole (123i)
The general procedure A was followed using 1-iodo-4-methylbenzene (1l) (2.18 g, 10.0 mmol), 1-hexyne (0.82 g, 10.0 mmol), NaN3 (0.68 g, 10.5 mmol), CuI (0.38 g, 1.0 mmol) and DMEDA (0.26 g, 1.5 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123i (1.64 g, 76%) as a colorless solid.
M.r.: 63−64 °C.
1H-NMR (300 MHz, CDCl3): δ = 7.65 (s, 1H), 7.56 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 2.84–2.70 (m, 2H), 2.38 (s, 3H), 1.77–1.61 (m, 2H), 1.40 (dq, J = 14.4, 7.3 Hz, 2H), 0.93 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 149.1 (Cq), 138.5 (Cq), 135.1 (Cq), 130.2 (CH), 120.4 (CH), 118.9 (CH), 31.7 (CH2), 25.5 (CH2), 22.4 (CH2), 21.0 (CH3), 13.8 (CH3).
IR (ATR): 𝑣̃ = 3130, 3085, 2922, 2869, 1523, 1456, 1320, 1230, 1198, 1120 cm-1. MS (ESI) m/z (relative intensity): 238 (20) [M+Na+], 216 (100) [M+H+].
HR-MS (ESI) m/z calcd for C13H18N3, [M+H+] 216.1495, found 216.1495.
Synthesis of 4-n-Butyl-1-(chlorophenyl)-1H-1,2,3-triazole (123j)
The general procedure A was followed using 1-chloro-4-iodobenzene (1m) (4.77 g, 20.0 mmol), 1-hexyne (1.64 g, 20.0 mmol), NaN3 (1.36 g, 21.0 mmol), CuI (0.38 g, 2.0 mmol) and DMEDA (0.26 g, 3.0 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123j (4.10 g, 87%) as a colorless solid.
M.r.: 73−74 °C.
1H-NMR (300 MHz, CDCl3): δ = 7.70–7.60 (m, 3H), 7.49–7.41 (m, 2H), 2.82–2.74 (m, 2H), 1.70 (dddd, J = 8.7, 7.6, 7.0, 5.8 Hz, 2H), 1.51–1.30 (m, 2H), 0.94 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 149.5 (Cq), 135.9 (Cq), 134.2 (Cq), 129.9 (CH), 121.6 (CH), 118.8 (CH), 31.6 (CH2), 25.4 (CH2), 22.4 (CH2), 13.9 (CH3).
IR (ATR): 𝑣̃ = 2961, 2927, 1498, 1462, 1403, 1224, 1092, 1047, 1010, 989 cm-1. MS (ESI) m/z (relative intensity): 274 (27) [M+K+], 258 (56) [M+Na+], 236 (100) [M+H+].
HR-MS (ESI) m/z calcd for C12H15ClN3, [M+H+] 236.0949, found 236.0938.
Synthesis of 4-n-Butyl-1-(4-methoxyphenyl)-1H-1,2,3-triazole (123k)
The general procedure A was followed using 1-iodo-4-methoxybenzene (1n) (2.34 g, 10.0 mmol), 1-hexyne (0.82 g, 10.0 mmol), NaN3 (0.68 g, 10.5 mmol), CuI (0.38 g, 1.0 mmol) and DMEDA (0.26 g, 1.5 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123k (2.10 g, 91%) as a colorless solid.
M.r.: 52−53 °C.
1H-NMR (300 MHz, CDCl3): δ = 7.62 (s, 1H), 7.57 (d, J = 9.1 Hz, 2H), 6.95 (d, J = 7.8, 7.8 Hz, 2H), 3.81 (s, 3H), 2.80–2.67 (m, 2H), 1.67 (dddd, J = 8.8, 7.6, 7.0, 5.7 Hz, 2H), 1.47–
1.32 (m, 2H), 0.94 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 159.6 (Cq), 148.9 (Cq), 130.8 (Cq), 122.0 (CH), 119.1 (CH), 114.5 (CH), 55.6 (CH3), 31.6 (CH2), 25.4 (CH2), 22.4 (CH2), 13.9 (CH3).
IR (ATR): 𝑣̃ = 3128, 2955, 2932, 2869, 1516, 1440, 1302, 1245, 1220, 1191 cm-1. MS (ESI) m/z (relative intensity): 254 (25) [M+Na+], 232 (100) [M+H+].
HR-MS (ESI) m/z calcd for C13H18N3O, [M+H+] 232.1444, found 232.1450.
Synthesis of Methyl 4-(4-n-butyl-1H-1,2,3-triazol-1-yl)benzoate (123l)
The general procedure A was followed using methyl 4-iodobenzoate (1o) (4.36 g, 20.0 mmol), 1-hexyne (1.64 g, 20.0 mmol), NaN3 (1.36 g, 21.0 mmol), CuI (0.38 g, 2.0 mmol) and DMEDA (0.26 g, 3.0 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123l (3.23 g, 74%) as a colorless solid.
M.p.: 111 °C.
1H-NMR (300 MHz, CDCl3): δ = 8.17 (d, J = 9.0 Hz, 2H), 7.82 (d, J = 8.9 Hz, 2H), 7.79 (s, 1H), 3.94 (s, 3H), 2.80 (ddd, J = 7.9, 7.3, 0.7 Hz, 2H), 1.71 (dddd, J = 8.7, 7.6, 7.0, 5.7 Hz, 2H), 1.50–1.34 (m, 2H), 0.94 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 166.1 (Cq), 149.7 (Cq), 140.4 (Cq), 131.4 (CH), 130.0 (Cq), 119.8 (CH), 118.7 (CH), 52.5 (CH3), 31.5 (CH2), 25.4 (CH2), 22.4 (CH2), 13.9 (CH3).
IR (ATR): 𝑣̃ = 3128, 2959, 2929, 2860, 1721, 1607, 1518, 1437, 1280, 1224 cm-1. MS (ESI) m/z (relative intensity): 298 (68) [M+K+], 282 (53) [M+Na+], 260 (100) [M+H+].
HR-MS (ESI) m/z calcd for C14H18N3O2, [M+H+] 260.1394, found 260.1388.
Synthesis of 4-n-Butyl-1-[3-(trifluoromethyl)phenyl]-1H-1,2,3-triazole (123m)
The general procedure A was followed using 1-iodo-3-(trifluoromethyl)benzene (1p) (5.44 g, 20.0 mmol), 1-hexyne (1.64 g, 20.0 mmol), NaN3 (1.36 g, 21.0 mmol), CuI (0.38 g, 2.0 mmol) and DMEDA (0.26 g, 3.0 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123m (4.68 g, 87%) as a colorless oil.
1H-NMR (300 MHz, CDCl3): δ = 8.01–7.82 (m, 1H), 7.78 (dd, J = 3.0, 0.7 Hz, 1H), 7.46–7.30 (m, 1H), 7.31–7.18 (m, 2H), 2.77 (ddd, J = 7.9, 7.3, 0.8 Hz, 2H), 1.69 (dddd, J = 8.8, 7.7, 7.1, 5.8 Hz, 2H), 1.50–1.26 (m, 2H), 0.93 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 149.8 (Cq), 137.7 (Cq), 132.5 (2JC-F = 33.2 Hz, Cq), 130.6 (CH), 125.1 (3JC-F = 3.7 Hz, CH), 123.5 (4JC-F = 1.2 Hz, CH), 123.5 (1JC-F = 273.2 Hz, Cq), 118.8 (CH), 117.3 (3JC-F = 3.9 Hz, CH), 31.6 (CH2), 25.4 (CH2), 22.4 (CH2), 13.9 (CH3).
19F-NMR (282 MHz, CDCl3): δ = -62.9 (s).
IR (ATR): 𝑣̃ = 3135, 3084, 2958, 2932, 2862, 1600, 1557, 1485, 1461, 1323 cm-1. MS (ESI) m/z (relative intensity): 292 (7) [M+Na+], 270 (100) [M+H+].
HR-MS (ESI) m/z calcd for C13H15F3N3, [M+H+] 270.1213, found 270.1212.
Syntheisis of 1-[3-(4-n-Butyl-1H-1,2,3-triazol-1-yl)phenyl]ethan-1-one (123n)
The general procedure A was followed using 1-(3-iodophenyl) ethan-1-one (1q) (2.46 g, 10.0 mmol), 1-hexyne (0.82 g, 10.0 mmol), NaN3 (0.68 g, 10.5 mmol), CuI (0.38 g, 1.0 mmol) and DMEDA (0.26 g, 1.5 mmol). Purification by column chromatography (n-pentane/EtOAc 5/1) yielded 123n (1.45 g, 60%) as an orange solid.
M.p.: 43 °C.
1H-NMR (300 MHz, CDCl3): δ = 8.69 (dd, J = 1.9, 1.9 Hz, 1H), 8.48–8.38 (m 2H), 8.23 (s, 1H), 8.0 (dd, J = 8.4 Hz, 1H), 3.40–3.17 (m, 2H), 3.10 (s, 3H), 2.27–2.05 (m, 2H), 1.86 (dq, J = 14.5, 7.3 Hz, 2H), 1.39 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 196.9 (Cq), 149.7 (Cq), 138.6 (Cq), 137.8 (Cq), 130.3 (CH), 128.2 (CH), 124.8 (CH), 119.6 (CH), 118.9 (CH), 31.6 (CH2), 26.9 (CH3), 25.5 (CH2), 22.4 (CH2), 13.9 (CH3).
IR (ATR): 𝑣̃ = 3139, 2957, 2928, 2857, 1682, 1604, 1556, 1490, 1398, 1287 cm-1. MS (ESI) m/z (relative intensity): 238 (16) [M+Na+], 244 (100) [M+H+].
HR-MS (ESI) m/z calcd for C14H18N3O, [M+H+] 244.1444, found 244.1450.
Synthesis of 3-(4-n-Butyl-1H-1,2,3-triazol-1-yl)-1-methyl-1H-indole (123o)
The general procedure A was followed using 3-iodo-1-methyl-1H-indole (1r) (3.86 g, 15.0 mmol), 1-hexyne (1,23 g, 15.0 mmol), NaN3 (1.02 g, 17.0 mmol), CuI (0.29 g, 1.5 mmol) and DMEDA (0.29 g, 2.3 mmol). Purification by column chromatography (n-pentane/EtOAc 9/1) yielded 123o (1.41 g, 37%) as a brown oil.
1H-NMR (300 MHz, CDCl3): δ = 7.76 (dd, J = 7.9, 1.0 Hz, 1H), 7.67 (s, 1H), 7.41 (d, J = 0.7 Hz, 1H), 7.38–7.27 (m, 2H), 7.25–7.17 (m, 1H), 3.82 (s, 3H), 2.88–2.73 (m, 2H), 1.82–1.65 (m, 2H), 1.45 (dq, J = 14.4, 7.3 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 148.3 (Cq), 135.6 (Cq), 123.2 (CH) 121.6 (CH), 121.3 (Cq), 121.0 (CH), 120.9 (CH), 118.6 (CH), 115.2 (Cq), 109.9 (CH), 33.2 (CH3), 31.7 (CH2), 25.5 (CH2), 22.5 (CH2), 13.7 (CH3).
IR (ATR): 𝑣̃ = 2954, 2929, 2858, 1730, 1615, 1478, 1447, 1334, 1247, 1213 cm-1. MS (ESI) m/z (relative intensity): 293 (85) [M+K+], 277 (18) [M+Na+], 255 (100) [M+H+].
HR-MS (ESI) m/z calcd for C15H18N4, [M+H+] 255.1604, found 255.1591.
Synthesis of Pyren-1-amine (123pa)
A suspension of 1-nitropyrene (5.55 g, 22 mmol) and palladium on carbon (0.58 g) in EtOAc (85 mL) and HOAc (7 mL, 17.4 M) was stired under a H2 atmosphere over night at ambient temperature. The reaction mixture was filtered over celite and the solvent was evaporated under reduced pressure. Purification by column chromatography (DCM/n-pentane 1/1) yielded 123pa (4.16 g, 84%) as a green solid.
M.r.: 124−125 °C.
1H-NMR (300 MHz, CDCl3): δ = 8.07 (ddd, J = 7.6, 5.8, 1.3 Hz, 2H), 8.03–7.88 (m, 5H), 7.84 (d, J = 8.9 Hz, 1H), 7.35 (d, J = 8.2 Hz, 1H), 4.44 (brs, 2H).
13C-NMR (125 MHz, CDCl3): δ = 141.0 (Cq), 132.3 (Cq), 131.8 (Cq), 127.7 (CH), 126.1 (CH), 126.1 (CH), 126.1 (CH), 126.1 (Cq), 125.6 (Cq), 124.4 (Cq), 124.2 (CH), 123.8 (CH), 123.6 (CH), 120.2 (CH), 117.0 (Cq), 114.1 (CH).
IR (ATR): 𝑣̃ = 3321, 3206, 3027, 1616, 1598, 1508, 1483, 1432, 1334, 1270 cm-1.
MS (EI) m/z (relative intensity): 217 (100) [M+], 200 (3), 189 (32), 163 (3), 108 (9), 94 (9), 81 (3), 63 (2), 58 (4), 43 (12).
HR-MS (EI) m/z calcd for C16H11N, [M+] 217.0891, found 217.0889.
Synthesis of 1-Azidopyren (123pb)
A suspension of pyren-1-amine (4.00 g, 18 mmol) in EtOAc (30 mL) was cooled to 0 °C. HCl (8 mL, 33 M) was added to the reaction mixture at 0 °C. A solution of sodium nitrite (1.66 g, 25 mmol) in H2O (20 mL) was added dropwise to the cooled reaction mixture over 10 minutes and was stirred for 1 h. Then NaN3 in H2O (20 mL) was added to the suspension and stirred for further 4 h at ambient temperatures. The reaction mixture was extracted with
EtOAc (3 x 50 mL), dried over Na2SO4.After filtration and evaporation of the solventin vacuo, the crude brown product was used without further purification in the next step.
M.r.: 113−114 °C.
A suspension of 1-azidopyren (4.42 g, 18 mmol), 1-hexyne (1.64 g, 20.0 mmol), CuI (0.38 g, 2.0 mmol) and DMEDA (0.26 g, 3.0 mmol) in DMSO (20 mL) and H2O (5 mL) was stirred at 55 °C over night. The reaction mixture was extracted with CH2Cl2 (3 x 50 mL). Purification by column chromatography (n-pentane/EtOAc 9/1) yielded 123p (0.48 g, 8%) as a brown solid.
M.r.: 103−104 °C.
MS (EI) m/z (relative intensity): 325 (3) [M+], 297 (40), 254 (100), 241 (8), 227 (16), 216 (10), 201 (61), 174 (3), 150 (2), 127 (5), 100 (7), 58 (3), 43 (8).
HR-MS (EI) m/z calcd for C22H19N3, [M+] 325.1597, found 325.1573.
Synthesis of Ethyl tolyl)-1H-1,2,3-triazole-4-carboxylate (123q) and Ethyl 1-(o-tolyl)-1H-1,2,3-triazole-5-carboxylate (123r)
In a 25 mL microwave flask a mixture of 1-azido-2-methylbenzene (0.67 g, 5 mmol) and ethyl propionate (5.00 g, 50 mmol) were stirred at 100 °C (50W) for 1.5 h. Purification by column chromatography (n-pentane/EtOAc 9/1) yielded 123q (0.05 g, 43%) and 123r (0.15 g, 13%) as orange oils.105
1H-NMR (300 MHz, CDCl3): δ = 8.27 (s, 1H), 7.50–7.29 (m, 4H), 4.27 (q, J = 7.1 Hz, 2H), 2.23 (s, 3H), 1.44 (t, J = 7.1 Hz, 3H).
13C-NMR (125 MHz, CDCl3): δ = 160.9 (Cq), 140.4 (Cq), 135.9 (Cq), 133.8 (Cq), 131.7 (CH), 130.6 (CH), 130.1 (CH), 129.1 (CH), 127.2 (CH), 61.6 (CH2), 18.0 (CH3), 14.5 (CH3).
IR (ATR): 𝑣̃ = 3133, 2982, 1719, 1541, 1503, 1374, 1335, 1292, 1244, 1226 cm-1.
MS (EI) m/z (relative intensity): 231 (7) [M+], 186 (8), 175 (8), 158 (23), 144 (12), 130 (100), 118 (15), 103 (15), 91 (47), 77 (19), 65 (45), 51 (11), 43 (13).
HR-MS (EI) m/z calcd for C12H13N3O2, [M+] 231.1008, found 231.1014.
1H-NMR (400 MHz, CDCl3): δ = 8.29 (s, 1H), 7.46 (dddd, J = 7.3, 1.4, 0.4 Hz, 1H), 7.39–7.21 (m, 2H), 7.26–7.21 (m, 1H), 4.24 (q, J = 7.1 Hz, 2H), 2.02 (s, 3H), 1.22 (t, J = 7.1 Hz, 3H).
13C-NMR (100 MHz, CDCl3): δ = 157.7 (Cq), 137.7 (CH), 136.2 (Cq), 135.2 (Cq), 130.9 (CH), 130.6 (CH), 130.1 (Cq), 127.1 (CH), 126.6 (CH), 61.9 (CH2), 17.3 (CH3), 13.4 (CH3).
IR (ATR): 𝑣̃ = 2981, 1730, 1499, 1464, 1367, 1307, 1291, 1277, 1184, 1048 cm-1.
MS (EI) m/z (relative intensity): 231 (30) [M+], 174 (4), 158 (23), 144 (8), 130 (100), 118 (22), 103 (26), 91 (43), 77 (35), 65 (29), 51 (12), 43 (16).
HR-MS (EI) m/z calcd for C12H13N3O2, [M+] 231.1008, found 231.1009.
Synthesis of 1-Phenyl-1H- 4-n-Butyl-1H-benzo[d]1,2,3-triazole (123s)
To a 250-mL schlenk flask, containing a magnetic stirring bar and equipped with an air condenser (without water circulation), were added Fe2O3 (399 mg, 10 mol %), 1H-benzo[d][1,2,3]triazole (2,98 mg, 25 mmol), t-BuOK (5.60 g, 50 mmol), DMSO (75 mL), and iodobenzene 1c (10,2 g, 50 mmol) in an open atmosphere. The contents were stirred for 24 h at 120 °C and allowed to cool to 25 °C. The mixture was diluted with EtOAc (25 mL) and H2O (25 mL) and stirring was continued for a further 10 min. The organic layer was separated and the aqueous layer was extracted with EtOAc (3 × 50 mL). The combined organic extracts were washed with H2O, brine and were dried over Na2SO4. The solvent was evaporated and the residue was purified by column chromatography (n-pentane/EtOAc 9/1) to give 147c (1.44 g, 30%) as an orange solid.
M.r.: 90−91 °C.
1H-NMR (400 MHz, CDCl3): δ = 8.16 (dd, J = 8.4, 1.0 Hz, 1H), 7.83–7.78 (m 2H), 7.76 (dd, J = 8.4, 1.0 Hz, 1H), 7.66–7.59 (m 2H), 7.58–7.48 (m 2H), 7.44 (ddd, J = 8.4, 7.0, 1.0 Hz, 1H).
13C-NMR (100 MHz, CDCl3): δ = 146.7 (Cq), 137.2 (Cq), 132.5 (Cq), 130.0 (CH), 128.8 (CH), 128.4 (CH), 124.5 (CH), 123.0 (CH), 120.5 (CH), 110.5 (CH).
IR (ATR): 𝑣̃ = 3057, 1595, 1499, 1459, 1447, 1384, 1326, 1291, 1276, 1089 cm-1. MS (ESI) m/z (relative intensity): 218 (25) [M+Na+], 196 (100) [M+H+].
HR-MS (ESI) m/z calcd for C12H10N3, [M+H+] 196.0869, found 196.0871.
The spectral data are in accordance with those reported in the literature.112
5.3.2 Synthesis of N-Tosylbenzamides