PAPER
5-Substituted 1H-Tetrazoles from Aldehydes
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mixture was cooled to r.t. and neutralized (pH 7) with 5% HCl.
Next, the mixture was extracted with EtOAc and the organic layer
was separated, dried (anhyd Na2SO4), and concentrated under re-
duced pressure. The crude product obtained was purified by column
chromatography (silica gel 100–200 mesh, EtOAc–hexane, 1:2)
to obtain 2a as a white solid; yield: 0.6 g (87%); mp 215–216 °C
(Lit.9e 215–216 °C).
HRMS (ESI): m/z [M + H] calcd for C8H6F3N4: 215.0545; found:
215.0549.
4-(1H-Tetrazol-5-yl)phenol (2f)
White solid; yield: 0.55 g (83%); mp 234–235 °C (Lit.9o 234–236
°C).
IR (KBr): 3442, 3397, 3227, 2983, 2839, 1544, 1459, 1322, 1232,
1141, 1028 cm–1.
1H NMR (300 MHz, DMSO): δ = 9.80 (s, 1 H), 7.72 (d, J = 8.6 Hz,
2 H), 6.92 (d, J = 8.6 Hz, 2 H).
IR (KBr): 3448, 3128, 3055, 1853, 1638, 1562, 1485, 1407, 1254,
1056 cm–1.
1H NMR (300 MHz, DMSO): δ = 8.10–8.05 (m, 2 H), 7.57–7.50 (m,
13C NMR (75 MHz, DMSO): δ = 162.2, 132.5, 130.7, 127.3, 114.6.
3 H).
13C NMR (75 MHz, DMSO): δ = 154.2, 129.5, 127.7, 125.6, 123.0.
MS (ESI): m/z = 163 [M + H].
MS (ESI): m/z = 147 [M + H].
HRMS (ESI): m/z [M + H] calcd for C7H7N4O: 163.0620; found:
163.0614.
HRMS (ESI): m/z [M + H] calcd for C7H7N4: 147.0671; found:
147.0665.
(E)-5-Styryl-1H-tetrazole (2g)
White solid; yield: 0.51 g (79%); mp 154–156 °C (Lit.9o 155–156
°C).
5-(4-Chlorophenyl)-1H-tetrazole (2b)
Brown solid; yield: 0.55 g (85%); mp 264–266 °C (Lit.9g 265–266
°C)
IR (KBr): 3391, 3058, 2991, 1617, 1586, 1494, 1345, 1208, 1145
cm–1.
1H NMR (300 MHz, DMSO): δ = 7.71 (d, J = 16.6 Hz, 1 H), 7.59–
7.57 (m, 2 H), 7.45–7.37 (m, 3 H), 7.16 (d, J = 16.6 Hz, 1 H).
IR (KBr): 3423, 3066, 2924, 1908, 1608, 1558, 1433, 1256, 1094
cm–1.
1H NMR (300 MHz, DMSO): δ = 10.20 (br s, 1 H), 8.10 (d, J = 8.5
Hz, 2 H), 7.47 (d, J = 8.5 Hz, 2 H).
13C NMR (75 MHz, DMSO): δ = 136.1, 133.2, 127.7, 127.1, 125.5,
13C NMR (75 MHz, DMSO): δ = 155.7, 135.0, 129.3, 128.4, 124.5.
108.6.
MS (ESI): m/z = 173 [M + H].
MS (ESI): m/z = 181 [M + H].
HRMS (ESI): m/z [M + H] calcd for C9H9N4: 173.0827; found:
173.0822.
HRMS (ESI): m/z [M + H] calcd for C7H6ClN4: 181.0281; found:
181.0279.
5-(1-Phenylethyl)-1H-tetrazole (2h)
Yellow solid; yield: 0.49 g (76%); mp 120–121 °C.
5-(4-Nitrophenyl)-1H-tetrazole (2c)
Yellow solid; yield: 0.44 g (70%); mp 218–219 °C (Lit.9o 220 °C).
IR (KBr): 3444, 2979, 1885, 1652, 1553, 1451, 1382, 1248, 1120,
1053 cm–1.
1H NMR (300 MHz, DMSO): δ = 7.33–7.23 (m, 5 H), 4.50–4.46 (q,
J = 7.8 Hz, 6.8 Hz, 1 H), 1.77 (d, J = 6.8 Hz, 3 H).
13C NMR (75 MHz, DMSO): δ = 128.2, 127.7, 127.3, 126.8, 126.2,
34.4, 19.4.
IR (KBr): 3443, 3106, 2924, 1604, 1514, 1452, 1347, 1292, 1102
cm–1.
1H NMR (300 MHz, DMSO): δ = 8.36 (d, J = 9.0 Hz, 2 H), 7.89 (d,
J = 9.0 Hz, 2 H).
13C NMR (75 MHz, DMSO): δ = 149.8, 146.6, 126.7, 115.1, 113.6.
MS (ESI): m/z = 192 [M + H].
MS (ESI): m/z = 175 [M + H].
HRMS (ESI): m/z [M + H] calcd for C7H6N5O2: 192.0521; found:
192.0524.
HRMS (ESI): m/z [M + H] calcd for C9H11N4: 175.0984; found:
175.0989.
5-(3,4-Dimethoxyphenyl)-1H-tetrazole (2d)
5-(Bicyclo[2.2.1]hept-5-en-2-yl)-1H-tetrazole (2i)
Brown solid; yield: 0.50 g (80%); mp 198–200 °C.
Yellow solid: yield: 0.43 g (65%); mp 145–146 °C.
IR (KBr): 3445, 3013, 2923, 2737, 1566, 1434, 1322, 1272, 1143,
1023 cm–1.
1H NMR (300 MHz, DMSO): δ = 7.69–7.67 (m, 2 H), 6.99 (d, J =
8.3 Hz, 1 H), 3.96–3.94 (6 H).
13C NMR (75 MHz, DMSO): δ = 154.9, 150.6, 119.7, 116.2, 110.7,
IR (KBr): 3451, 3065, 1861, 1633, 1571, 1452, 1338, 1260, 1133,
1024 cm–1.
1H NMR (300 MHz, DMSO): δ = 6.33–6.31 (m, 1 H), 6.19–6.15 (m,
1 H), 3.04–3.19 (m, 1 H), 2.86–2.82 (m, 1 H), 2.20–2.11 (m, 1 H),
1.57–1.49 (m, 2 H), 1.33–1.29 (m, 1 H), 1.21–1.19 (m, 1 H).
13C NMR (75 MHz, DMSO): δ = 138.8, 137.2, 122.9, 47.7, 45.7,
42.3, 32.4, 27.02.
109.5, 55.4, 55.3.
MS (ESI): m/z = 207 [M + H].
HRMS (ESI): m/z [M + H] calcd for C9H11N4O2: 207.2092; found:
207.2097.
MS (ESI): m/z = 163 [M + H].
HRMS (ESI): m/z [M + H] calcd for C8H11N4: 163.0984; found:
163.0988.
5-[4-(Trifluoromethyl)phenyl]-1H-tetrazole (2e)
White solid; yield: 0.37 g (60%); mp 219–220 °C (Lit.9e 220–221
°C).
5-(Cyclohex-3-enyl)-1H-tetrazole (2j)
Yellow solid; yield: 0.54 g (79%); mp 127–128 °C.
IR (KBr): 3422, 3021, 2965, 1597, 1450, 1386, 1296, 1125, 1098
cm–1.
1H NMR (300 MHz, DMSO): δ = 8.14 (d, J = 8.5 Hz, 2 H), 7.69 (d,
J = 8.5 Hz, 2 H).
IR (KBr): 3445, 3117, 3030, 1868, 1654, 1557, 1431, 1353, 1252,
1114 cm–1.
1H NMR (300 MHz, DMSO): δ = 5.85– 5.71 (m, 2 H), 3.32–3.20
(m, 1 H), 2.58–2.32 (m, 2 H), 2.21–2.12 (m, 3 H), 1.91–1.81 (m, 1
H).
13C NMR (75 MHz, DMSO): δ = 166.3, 133.8, 129.4, 126.9, 124.5.
MS (ESI): m/z = 215 [M + H].
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 507–510