Full Paper
3-(4-Ethylphenoxy)-1,2,4-triazine (13e): Column chromatography
(50 % ethyl acetate in hexanes) afforded 13e (0.511 g, 81 % yield)
1H NMR (400 MHz, CDCl3): δ = 8.90–8.89 (d, J = 2.2 Hz, 1 H), 8.40–
8.39 (d, J = 2.2 Hz, 1 H), 5.49–5.42 (sept, J = 6.2 Hz, 1 H), 1.44–1.43
as a yellow liquid. IR (neat): ν = 810, 845, 891, 1015, 1045, 1107, (d, J = 6.2 Hz, 7 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 165.2,
˜
1165, 1196, 1312, 1358, 1400, 1458, 1505, 1551, 2870, 2928,
151.0, 144.5, 72.1, 21.8 ppm. HRMS (EI): calcd. for C6H9N3O [M + H]+
1
2963 cm–1. H NMR (400 MHz, CDCl3): δ = 9.05 (d, J = 2.3 Hz, 1 H), 140.0818; found 140.0818.
8.45 (d, J = 2.3 Hz, 1 H), 7.29–7.26 (m, 2 H), 7.16–7.13 (m, 2 H), 2.73–
3-(2-Methoxyethoxy)-1,2,4-triazine (13l): Column chromatogra-
phy (ethyl acetate) afforded 13l (0.337 g, 69 % yield) as a yellow
2.66 (q, J = 7.6 Hz, 2 H), 1.28–1.25 (t, J = 7.6 Hz, 3 H) ppm. 13C NMR
(101 MHz, CDCl3): δ = 166.6, 150.9, 150.3, 145.7, 142.2, 129.3, 121.2,
28.4, 15.6 ppm. HRMS (EI): calcd. for C11H11N3O [M + H]+ 202.0975;
found 202.0969.
solid; m.p. 68–70 °C. IR (neat): ν = 853, 880, 930, 1007, 1042, 1057,
˜
1099, 1126, 1157, 1192, 1238, 1281, 1327, 1346, 1373, 1400, 1431,
1454, 1539, 1555, 2816, 2839, 2905, 2936, 2997, 3051, 3094 cm–1
.
3-(4-Fluorophenoxy)-1,2,4-triazine (13f): Column chromatogra- 1H NMR (400 MHz, [D6]DMSO): δ = 9.15 (d, J = 2.3 Hz, 1 H), 8.68 (d,
phy (50 % ethyl acetate in hexanes) afforded 13f (0.467 g, 78 %
J = 2.3 Hz, 1 H), 4.59–4.56 (m, 2 H), 3.74–3.71 (m, 2 H), 3.31 (s, 3 H)
ppm. 13C NMR (101 MHz, [D6]DMSO): δ = 165.1, 152.1, 145.7, 69.7,
67.0, 58.1 ppm. HRMS (EI): calcd. for C6H9N3O2 [M + H]+ 156.0768;
found 156.0760.
yield) as a yellow solid; m.p. 59–61 °C. IR (neat): ν = 823, 841, 868,
˜
899, 1007, 1053, 1092, 1180, 1323, 1370, 1404, 1501, 1535, 1555,
1
3078 cm–1. H NMR (400 MHz, CDCl3): δ = 9.08–9.07 (d, J = 2.3 Hz,
1 H), 8.47–8.46 (d, J = 2.3 Hz, 1 H), 7.23–7.18 (m, 2 H), 7.16–7.10 (m,
2 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 116.7, 123.0, 146.0, 148.2,
151.0, 160.5, 166.4 ppm. 19F NMR (376 MHz, CDCl3): δ = –116.4
(s) ppm. HRMS (EI): calcd. for C9H6FN3O [M + H]+ 192.0568; found
192.0563.
2-[(1,2,4-Triazin-3-yl)oxy]-N,N-dimethylethan-1-amine (13m):
Column chromatography (5 % methanol in dichloromethane) af-
forded 13m (0.337 g, 64 % yield) as a yellow liquid. IR (neat): ν =
˜
833, 864, 918, 953, 991, 1026, 1099, 1153, 1192, 1319, 1339, 1373,
1424, 1458, 1520, 1551, 1670, 2770, 2820, 2947, 3414 cm–1. 1H NMR
3-(Benzyloxy)-1,2,4-triazine (13g): Column chromatography (400 MHz, [D6]DMSO): δ = 9.13–9.12 (d, J = 2.3 Hz, 1 H), 8.67–8.66
(50 % ethyl acetate in hexanes) afforded 13g (0.470 g, 80 % yield)
(d, J = 2.3 Hz, 1 H), 4.53–4.51 (t, J = 5.8 Hz, 2 H), 2.68–2.65 (t, J =
5.8 Hz, 2 H), 2.20 (s, 6 H) ppm. 13C NMR (101 MHz, [D6]DMSO): δ =
165.1, 152.0, 145.5, 65.7, 57.2, 45.4 ppm. HRMS (EI): calcd. for
as a yellow solid; m.p. 67–69 °C. IR (neat): ν = 880, 988, 1026, 1103,
˜
1165, 1231, 1323, 1359, 1381, 1416, 1454, 1493, 1543, 2886, 2955,
3024, 3086 cm–1 1H NMR (400 MHz, [D6]DMSO): δ = 9.17 (d, J = C7H12N4O [M + H]+ 169.1084; found 169.1086.
.
2.3 Hz, 1 H), 8.71 (d, J = 2.3 Hz, 1 H), 7.52–7.50 (m, 2 H), 7.43–7.34
(m, 3 H), 5.54 (s, 2 H) ppm. 13C NMR (101 MHz, [D6]DMSO): δ =
165.0, 152.2, 145.8, 135.9, 128.5, 128.3, 128.3, 69.3 ppm. HRMS (EI):
calcd. for C10H9N3O [M + H]+ 188.0818; found 188.0816.
5-{2-[(1,2,4-Triazin-3-yl)oxy]ethyl}-4-methylthiazole (13n): Col-
umn chromatography (ethyl acetate) afforded 13n (0.428 g, 61 %
yield) as a yellow solid; m.p. 103–105 °C. IR (neat): ν = 837, 876,
˜
918, 988, 1011, 1042, 1107, 1161, 1188, 1297, 1316, 1350, 1408,
1
3-[2-(Trimethylsilyl)ethoxy]-1,2,4-triazine (13h): Column chroma-
tography (50 % ethyl acetate in hexanes) afforded 13h (0.507 g,
1435, 1458, 1532, 1555, 3040 cm–1. H NMR (400 MHz, [D6]DMSO):
δ = 9.15–9.14 (d, J = 2.3 Hz, 1 H), 8.84 (s, 1 H), 8.68–8.67 (d, J =
2.3 Hz, 1 H), 4.64–4.61 (t, J = 6.4 Hz, 2 H), 3.33–3.30 (t, J = 6.4 Hz, 2
H), 2.34 (s, 3 H) ppm. 13C NMR (101 MHz, [D6]DMSO): δ = 164.9,
82 % yield) as a yellow liquid. IR (neat): ν = 833, 937, 961, 1015,
˜
1038, 1099, 1153, 1177, 1246, 1319, 1343, 1378, 1431, 1470, 1520,
1551, 1697, 2897, 2951 cm–1 1H NMR (400 MHz, [D6]DMSO): δ = 152.2, 150.9, 149.6, 145.8, 127.0, 67.8, 25.2, 14.7 ppm. HRMS (EI):
.
9.11 (d, J = 2.3 Hz, 1 H), 8.65 (d, J = 2.3 Hz, 1 H), 4.57–4.53 (m, 2 H),
1.19–1.15 (m, 2 H), 0.06 (s, 9 H) ppm. 13C NMR (101 MHz, [D6]DMSO):
δ = 165.0, 151.9, 145.4, 66.0, 16.8, 2.0, –1.5 ppm. HRMS (EI): calcd.
for C8H15N3OSi [M + H]+ 198.1057; found 198.1062.
calcd. for C9H10N4OS [M + H]+ 223.0648; found 223.0653.
3-Cyclopropoxy-1,2,4-triazine (13o): Column chromatography
(50 % ethyl acetate in hexanes) afforded 13o (0.227 g, 53 % yield)
as a yellow liquid. IR (neat): ν = 826, 860, 964, 1026, 1045, 1096,
˜
3-(Prop-2-yn-1-yloxy)-1,2,4-triazine (13i): Column chromatogra-
phy (50 % ethyl acetate in hexanes) afforded 13i (0.332 g, 78 %
1146, 1165, 1211, 1335, 1373, 1412, 1451, 1532, 1551, 1593, 3017,
1
3098 cm–1. H NMR (400 MHz, CDCl3): δ = 8.98 (d, J = 2.2 Hz, 1 H),
yield) as a yellow solid; m.p. 51–53 °C. IR (neat): ν = 876, 964, 988,
8.42 (d, J = 2.2 Hz, 1 H), 4.51–4.46 (m, 1 H), 0.89–0.86 (m, 4 H) ppm.
˜
1018, 1053, 1103, 1157, 1316, 1346, 1366, 1424, 1474, 1539, 1555,
13C NMR (101 MHz, CDCl3): δ = 166.6, 150.8, 145.2, 52.8, 6.0 ppm.
2129, 2943, 2963, 3051, 3094, 3240 cm–1. 1H NMR (400 MHz, CDCl3): HRMS (EI): calcd. for C6H7N3O [M + H]+ 138.0662; found 138.0659.
δ = 9.03–9.02 (d, J = 2.3 Hz, 1 H), 8.49–8.48 (d, J = 2.3 Hz, 1 H),
2-[(1,2,4-Triazin-3-yl)oxy]-N,N-dimethylpropan-1-amine (13p):
Column chromatography (5 % methanol in dichloromethane) af-
5.20–5.19 (d, J = 2.4 Hz, 2 H), 2.54–2.53 (t, J = 2.4 Hz, 1 H) ppm. 13
C
NMR (101 MHz, CDCl3): δ = 164.8, 151.1, 145.6, 77.4, 75.9, 56.2 ppm.
forded 13p (0.296 g, 52 % yield) as a yellow liquid. IR (neat): ν =
˜
HRMS (EI): calcd. for C6H5N3O [M + H]+ 136.0505; found 136.0502.
837, 856, 945, 1038, 1099, 1134, 1153, 1207, 1265, 1319, 1331, 1373,
3-(3,3,3-Trifluoropropoxy)-1,2,4-triazine (13j): Column chroma-
tography (50 % ethyl acetate in hexanes) afforded 13j (0.451 g,
1420, 1520, 1551, 1670, 2770, 2820, 2940, 2978 cm–1 1H NMR
.
(400 MHz, [D6]DMSO): δ = 9.10 (d, J = 2.3 Hz, 1 H), 8.65 (d, J =
2.3 Hz, 1 H), 5.45–5.40 (m, 1 H), 2.64–2.59 (dd, J = 12.9, 7.3 Hz, 1 H),
2.43–2.38 (dd, J = 12.9, 4.9 Hz, 1 H), 2.18 (s, 6 H), 1.34–1.32 (d, J =
74 % yield) as a yellow liquid. IR (neat): ν = 826, 864, 910, 991, 1030,
˜
1045, 1072, 1130, 1150, 1250, 1296, 1323, 1362, 1389, 1431, 1470,
1524, 1535, 1555, 2920, 2974 cm–1. H NMR (400 MHz, CDCl3): δ = 6.2 Hz, 3 H) ppm. 13C NMR (101 MHz, [D6]DMSO): δ = 164.9, 151.9,
1
9.01 (d, J = 2.2 Hz, 1 H), 8.46 (d, J = 2.2 Hz, 1 H), 4.79–4.76 (t, J =
145.3, 72.0, 63.6, 45.8, 18.0 ppm. HRMS (EI): calcd. for C8H14N4O [M
6.5 Hz, 2 H), 2.79–2.68 (qt, J = 10.4, 6.5 Hz, 2 H) ppm. 13C NMR
+ H]+ 183.1240; found 183.1237.
(101 MHz, CDCl3): δ = 165.0, 151.3, 145.5, 124.8, 61.6, 33.6 ppm. 19
F
2-[(1,2,4-Triazin-3-yl)oxy]ethan-1-ol (13q): Column chromatogra-
phy (2 % methanol in dichloromethane) afforded 13q (0.144 g, 33 %
NMR (376 MHz, CDCl3): δ = –64.8 ppm. HRMS (EI): calcd. for
C6H6F3N3O [M + H]+ 194.0536; found 194.0531.
yield) as a yellow liquid. IR (neat): ν = 823, 868, 922, 1030, 1157,
˜
3-Isopropoxy-1,2,4-triazine (13k): Column chromatography (50 %
ethyl acetate in hexanes) afforded 13k (0.307 g, 70 % yield) as a
1319, 1339, 1377, 1424, 1462, 1524, 1555, 1690, 2947, 3333 cm–1
.
1H NMR (400 MHz, [D6]DMSO): δ = 9.14–9.13 (d, J = 2.3 Hz, 1 H),
yellow liquid. IR (neat): ν = 864, 949, 1015, 1049, 1103, 1153, 1180, 8.68–8.67 (d, J = 2.3 Hz, 1 H), 4.93 (br. s, 1 H), 4.48–4.46 (m, 2 H),
˜
1316, 1335, 1373, 1420, 1466, 1520, 1551, 2874, 2940, 2982 cm–1
.
3.79–3.76 (m, 2 H) ppm. 13C NMR (101 MHz, [D6]DMSO): δ = 165.2,
Eur. J. Org. Chem. 2016, 2842–2850
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim