G. Aridoss, K. K. Laali
FULL PAPER
= 215 (M + 1)+, 186 (100%), 167, 159, 145 (CF3 loss), 139, 109,
69.
H, Ar), 7.89 (dt, J = 7.8, J = 1.5 Hz, 1 H, Ar), 8.23 (dd, J = 8, J
= 1.5 Hz, 1 H, Ar), 8.97 (s, 1 H, -CH) ppm. 13C NMR (125 MHz,
CDCl3, 25 °C): δ = 126.34, 127.05, 128.84, 132.36, 134.79 (Ar),
143.62 (-CH), 144.09 (Ar) ppm.
1-(3-Nitrophenyl)-1H-1,2,3,4-tetrazole (16):[23] Off-white crystalline
solid; m.p. 105–106 °C. 1H NMR (500 MHz, CDCl3, 25 °C): δ =
7.86 (t, J = 8.24 Hz, 1 H, Ar), 8.18 (ddd, J = 8, J = 2.1, J = 1.1 Hz,
1 H, Ar), 8.47 (ddd, J = 8.5, J = 2.0, J = 1 Hz, 1 H, Ar), 8.64 (t,
J = 2.0 Hz, 1 H, Ar), 9.26 (s, 1 H, -CH) ppm. 13C NMR (125 MHz,
CDCl3, 25 °C): δ = 116.37, 124.67, 126.87, 131.74, 134.70 (Ar),
140.75 (-CH), 149.14 (C-NO2) ppm.
1-(4-Nitrophenyl)-1H-1,2,3,4-tetrazole (17):[23] Pale yellow solid;
m.p. 199–200 °C. 1H NMR (500 MHz, CDCl3 + 3 drops of
[D6]DMSO, 25 °C): δ = 7.98 (d, J = 9.5 Hz, 2 H, Ar), 8.27 (d, J =
9.5 Hz, 2 H, Ar), 9.65 (s, 1 H, -CH) ppm. 13C NMR (125 MHz,
CDCl3 + 3 drops of [D6]DMSO, 25 °C): δ = 121.14, 125.39, 137.98
(Ar), 141.18 (-CH), 147.43 (C-NO2) ppm.
1-(4-Trifluoromethylphenyl)-1H-1,2,3,4-tetrazole (8): Pale yellow
spongy solid; m.p. 152–153 °C. 1H NMR (500 MHz, CDCl3,
25 °C): δ = 7.80–7.92 (m, 4 H, Ar), 9.12 (s, 1 H, -CH) ppm. 13C
NMR (125 MHz, CDCl3, 25 °C): δ = 121.48 (Ar), 123.35 (q, JC,F
= 271.1 Hz, -CF3), 127.74 (q, JC,F = 3.8 Hz, Ar), 132.27 (q, JC,F
=
33.1 Hz, Ar), 136.44 (Ar), 140.58 (-CH) ppm. 19F NMR
(470.2 MHz, CDCl3, 25 °C): δ = –62.87 (s, -CF3) ppm. IR (in
CHCl ): ν = 3129, 3090, 1616, 1526, 1468, 1331, 1213, 1123, 1072
˜
3
cm–1. MS (EI): m/z = 215 (M + 1)+, 186 (100%, N2 loss), 167, 159,
145 (CF3 loss), 139, 109, 69 (CF3+).
1-(4-Methylphenyl)-1H-1,2,3,4-tetrazole (9):[11] White crystalline so-
1
lid; m.p. 94 °C. H NMR (500 MHz, CDCl3, 25 °C): δ = 2.43 (s, 3
H, -CH3), 7.36 (d, J = 8.5 Hz, 2 H, Ar), 7.57 (d, J = 8.5 Hz, 2 H,
Ar), 8.98 (s, 1 H, -CH) ppm. 13C NMR (125 MHz, CDCl3, 25 °C):
δ = 21.29 (-CH3), 121.21, 130.77, 131.54, 140.53* (Ar), 140.61*
(-CH) ppm; assignments marked with asterisks * are interchange-
able.
1-(4-Cyanophenyl)-1H-1,2,3,4-tetrazole (18): White crystalline so-
lid; m.p. 177–178 °C. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 7.85
(d, J = 9 Hz, 2 H, Ar), 7.95 (d, J = 8.5 Hz, 2 H, Ar), 9.4 (s, 1 H,
-CH) ppm. 13C NMR (125 MHz, CDCl3, 25 °C): δ = 113.64 (C-
CN), 117.30 (-CN), 121.40, 134.25, 136.83 (Ar), 140.83 (-CH) ppm.
1-(2-Methoxyphenyl)-1H-1,2,3,4-tetrazole (10):[9,10] (references do
1
not report melting point and NMR data): Brownish oil. H NMR
(500 MHz, CDCl3, 25 °C): δ = 3.94 (s, 3 H, -OCH3), 7.13–7.17 (m,
2 H, Ar), 7.48 (dt, J = 8.1, J = 1.5 Hz, 1 H, Ar), 7.82 (dd, J = 8.1,
J = 1.8 Hz, 1 H, Ar), 9.17 (s, 1 H, -CH) ppm. 13C NMR (125 MHz,
CDCl3, 25 °C): δ = 56.13 (-OCH3), 110.07, 112.42, 121.40, 124.60,
IR (in CH Cl ): ν = 3113, 2910, 2228 (CN), 1692, 1607, 1516, 1466,
˜
2
2
1215, 1088, 995, 843 cm–1. MS (EI): m/z = 146 (M+ – CN), 118
(100%), 91, 64, 52, 38.
130.95 (Ar), 143.15 (-CH), 150.62 (C-OCH3) ppm. IR (in CHCl3): 1-(4-Acetylphenyl)-1H-1,2,3,4-tetrazole (19):[12] Pale yellow solid;
ν = 3138, 2940, 2845, 1692, 1603, 1508, 1460, 1287 cm–1. MS (EI):
m.p. 176 °C. 1H NMR (500 MHz, CDCl3 + 2 drops of [D6]DMSO,
25 °C): δ = 2.52 (s, 3 H, -COCH3), 7.82 (d, J = 9 Hz, 2 H, Ar),
8.02 (d, J = 8.5 Hz, 2 H, Ar), 9.39 (s, 1 H, -CH) ppm. 13C NMR
(125 MHz, CDCl3 + 2 drops of [D6]DMSO, 25 °C): δ = 26.55
(-COCH3), 120.60, 130.09, 136.78, 137.48 (Ar), 140.80 (-CH),
196.15 (-COCH3) ppm.
2-(1H-1,2,3,4-Tetrazol-1-yl)benzoic Acid (20):[24] Spongy white so-
lid; m.p. 194–195 °C. 1H NMR (500 MHz, CDCl3 + 2 drops of
[D6]DMSO, 25 °C): δ = 7.39 (d, J = 7.5, J = 1.5 Hz; 1 H, Ar),
7.57–7.65 (m, 2 H, Ar), 8.27 (d, J = 7.5, J = 1.5 Hz; 1 H, Ar), 8.87
(s, 1 H, -CH) ppm. 13C NMR (125 MHz, CDCl3 + 2 drops of
[D6]DMSO, 25 °C): δ = 127.43, 127.79, 130.84, 132.02 (Ar), 132.90
(C-COOH), 132.97 (Ar), 144.10 (-CH), 165.74 (-COOH) ppm.
˜
m/z = 176 (M)+, 148 (N2 loss), 133, 120, 105 (100%), 78, 51.
1-(3-Methoxyphenyl)-1H-1,2,3,4-tetrazole (11):[21] Pale brown solid;
1
m.p. 71 °C. H NMR (500 MHz, CDCl3, 25 °C): δ = 3.90 (s, 3 H,
-OCH3), 7.06 (dd, J = 8.3, J = 2.3 Hz, 1 H, Ar), 7.25–7.30 (m, 2
H, Ar), 7.48 (t, J = 9.2 Hz, 1 H, Ar), 9.04 (s, 1 H, -CH) ppm. 13C
NMR (125 MHz, CDCl3, 25 °C): δ = 55.73 (-OCH3), 107.0, 112.89,
115.61, 130.98 (Ar), 140.76 (Ar & -CH), 160.73 (C-OCH3) ppm.
1-(4-Methoxyphenyl)-1H-1,2,3,4-tetrazole (12):[13] White solid; m.p.
115–116 °C. NMR (500 MHz, CDCl3, 25 °C): δ = 3.88 (s, 3 H,
-OCH3), 7.06 (d, J = 9.5 Hz, 2 H, Ar), 7.95 (d, J = 9.5 Hz, 2 H,
Ar), 8.92 (s, 1 H, -CH) ppm. 13C NMR (125 MHz, CDCl3, 25 °C):
δ = 55.79 (-OCH3), 115.34, 123.1, 128.78, 140.68 (Ar), 160.87 (C-
OCH3) ppm.
3-(1H-1,2,3,4-Tetrazol-1-yl)benzoic Acid (21): Off-white solid; m.p.
181–182 °C (dec.). 1H NMR (500 MHz, CDCl3 + 3 drops of
[D6]DMSO, 25 °C): δ = 7.47 (t, J = 8.0 Hz, 1 H, Ar), 7.81 (ddd, J
= 8, J = 2.5, J = 1 Hz, 1 H, Ar), 7.97 (dt, J = 8, J = 1.3 Hz, 1 H,
Ar), 8.82 (t, J = 1.8 Hz, 1 H, Ar), 9.30 (s, 1 H, -CH) ppm. 13C
NMR (125 MHz, CDCl3 + 4 drops of [D6]DMSO, 25 °C): δ =
121.64, 124.54, 129.92, 130.49, 133.04 (Ar), 133.64 (C-COOH),
2-[4-(1H-1,2,3,4-Tetrazol-1-yl)phenyl]acetic Acid (13): Pale yellow
solid; m.p. 150–151 °C. 1H NMR (500 MHz, CDCl3 + 1dp of
[D6]DMSO, 25 °C): δ = 3.58 (s, 2 H, -OCH2), 7.4 (d, J = 8.5 Hz, 2
H, Ar), 7.59 (d, J = 8.0 Hz, 2 H, Ar), 9.11 (s, 1 H, -CH) ppm. 13C
NMR (125 MHz, CDCl3 + 2 drops of [D6]DMSO, 25 °C): δ =
40.60 (-OCH2), 121.01, 131.06, 132.46, 136.76 (Ar), 140.71 (Ar),
140.78 (-CH), 166.35 (-COOH) ppm. IR (in CH Cl ): ν = 3098,
˜
2
2
3080, 2922, 2853, 1701, 1593, 1481, 1287 cm–1. MS (EI): m/z = 162
172.72 (C=O) ppm. IR (NaCl plate): ν = 3131, 2918, 1695, 1522,
˜
1414, 1254, 1209, 1092 cm–1. MS (EI): m/z = 177, 132, 77, 51, 45
(M+ – N2), 121, 92, 65 (100%), 52, 46, 38.
(100%).
1-(2-Pyridine)-1H-1,2,3,4-tetrazole (22):[11] White solid; m.p. 126–
1-(3-Hydroxyphenyl)-1H-1,2,3,4-tetrazole (14):[8] Pale yellow solid;
m.p. 174–175 °C. 1H NMR (500 MHz, CDCl3 + 2 drops of
[D6]DMSO, 25 °C): δ = 6.94 (ddd, J = 8.3, J = 2.4, J = 1 Hz, 1 H,
Ar), 7.09 (ddd, J = 7.9, J = 2, J = 1 Hz, 1 H, Ar), 7.19 (t, J =
2.2 Hz, 1 H, Ar), 7.30 (t, J = 8.1 Hz, 1 H, Ar), 9.00 (s, 1 H, -CH),
9.5 (br. s, 1 H, -OH) ppm. 13C NMR (125 MHz, CDCl3 + 2 drops
of [D6]DMSO, 25 °C): δ = 108.28, 111.30, 117.08, 130.67, 134.37
(Ar), 140.63 (-CH), 158.73 (C-OH) ppm.
1
127. H NMR (500 MHz, CDCl3, 25 °C): δ = 7.45 (ddd, J = 7.5,
J = 5, J = 1 Hz, 1 H, Ar), 8.0 (ddd, J = 8.5, J = 7, J = 1.5 Hz, 1
H, Ar), 8.09 (dt, J = 9, J = 1 Hz, 1 H, Ar), 8.55 (ddd, J = 5, J =
2, J = 1 Hz, 1 H, Ar), 9.54 (s, 1 H, -CH) ppm. 13C NMR (125 MHz,
CDCl3, 25 °C): δ = 114.53, 124.92, 139.93 (Ar), 140.21 (-CH),
147.06, 149.19 (Ar) ppm.
1-Benzyl-1H-1,2,3,4-tetrazole (23):[11] White crystalline solid; m.p.
58 °C. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 5.6 (s, 2 H, -CH2),
7.28–7.3 (m, 2 H, Ar), 7.39–7.4 (m, 3 H, Ar), 8.53 (s, 1 H, -CH)
1-(2-Nitrophenyl)-1H-1,2,3,4-tetrazole (15):[22] Yellow crystalline
solid; m.p. 66 °C. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 7.63 ppm. 13C NMR (125 MHz, CDCl3, 25 °C): δ = 52.29 (-CH2),
(dd, J = 8, J = 1.5 Hz, 1 H, Ar), 7.83 (dt, J = 7.8, J = 1.2 Hz, 1
128.41, 129.49, 129.53, 132.93 (Ar), 142.51 ppm.
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Eur. J. Org. Chem. 2011, 2827–2835