The Journal of Organic Chemistry
Article
1-(4-Methoxyphenyl)-N-(4-nitrophenyl)-1H-tetrazol-5-amine
(7e). Following the general procedure A, compound 7e was obtained
after dry-flash column chromatography (SiO2: Hex/EtOAc = 7/3) as
a yellow powder (47 mg, 60%) from 5b (50 mg, 0.26 mmol) and 6c
(50 mg, 0.25 mmol); mp 237 °C. IR (ATR): 3071, 3935, 1620, 1584,
1535, 1512, 1334, 1258, 1108, 749 cm−1. 1H NMR (400 MHz,
DMSO-d6): δ 10.06 (s, 1H), 8.24 (d, J = 9.2 Hz, 2H), 7.86 (d, J = 9.2
Hz, 2H), 7.62 (d, J = 8.8 Hz, 2H), 7.19 (d, J = 8.8 Hz, 2H), 3.87 (s,
3H) ppm. 13C{1H} NMR (100 MHz, DMSO-d6): δ 160.6, 151.8,
146.4, 141.0, 127.7, 125.3, 125.2, 117.4, 115.0, 55.7 ppm. HRMS
(55 μL, 0.53 mmol); mp 109−110 °C. IR (ATR) 3429, 3201, 3085,
3044, 2993, 2925, 1604, 1571, 1534, 1494, 1466, 1451, 1401, 1321,
1268, 1243, 1198, 1153, 1084, 1034, 1006, 984, 890, 865, 795, 747,
1
688, 523 cm−1. H NMR (400 MHz, DMSO-d6): δ 9.38 (s, 1H),
7.74−7.60 (m, 4H), 7.57−7.47 (m, 2H), 7.37−7.29 (m, 2H), 7.05−
6.99 (m, 1H) ppm. 13C{1H} NMR (100 MHz, DMSO-d6): δ 162.2
(d, J = 244 Hz), 152.4, 139.7, 134.2 (d, J = 11 Hz), 131.7 (d, J = 9
Hz), 128.8, 122.2, 122.1 (d, J = 4 Hz), 118.4, 117.1 (d, J = 21 Hz),
113.5 (d, J = 25 Hz) ppm. HRMS (HESI/Orbitrap) m/z: [M + H]+
+
calcd for C13H11FN5 , 256.0993; found, 256.0996.
+
(HESI/Orbitrap) m/z: [M + H]+ calcd for C14H13N6O3 , 313.1044;
N-(4-Fluorophenyl)-1-phenyl-1H-tetrazol-5-amine (7k). Follow-
ing the general procedure A, compound 7k was obtained after dry-
flash column chromatography (SiO2: Hex/EtOAc = 8/2) as an off-
white powder (110 mg, 81%) from 5a (100 mg, 0.559 mmol) and 6f
(55 μL, 0.53 mmol); mp 165−167 °C. IR (ATR): 3244, 3213, 3178,
3126, 3069, 3038, 3001, 2961, 2912, 2826, 2773, 1620, 1575, 1502,
1456, 1439, 1393, 1325, 1211, 1158, 1125, 1094, 1070, 1045, 1019,
992, 847, 814, 790, 770, 729, 692, 643, 621, 585, 506 cm−1. 1H NMR
(400 MHz, DMSO-d6): δ 9.35 (s, 1H), 7.84−7.44 (m, 7H), 7.24−
7.10 (m, 2H) ppm. 13C{1H} NMR (100 MHz, DMSO-d6): δ 157.5
(d, J = 237 Hz), 152.4, 136.2 (d, J = 2 Hz), 133.0, 130.1, 129.9, 125.6,
120.2 (d, J = 8 Hz), 115.3 (d, J = 23 Hz) ppm. HRMS (HESI/
found, 313.1051.
N-(4-Methoxyphenyl)-1-(4-nitrophenyl)-1H-tetrazol-5-amine
(7f). Following the general procedure A, compound 7f was obtained
after dry-flash column chromatography (SiO2: Hex/EtOAc = 7/3) as
an orange powder (58 mg, 74%) from 5c (54 mg, 0.26 mmol) and 6a
(31 μL, 0.25 mmol); mp 98−99 °C. IR (ATR): 3278, 3086, 2959,
2927, 2856, 1727, 1616, 1577, 1511, 1463, 1340, 1295, 1257, 1113,
1
1077, 1032, 854, 746 cm−1. H NMR (400 MHz, DMSO-d6): δ 9.34
(s, 1H), 8.48 (d, J = 9.0 Hz, 2H), 8.01 (d, J = 9.0 Hz, 2H), 7.50 (d, J =
9.0 Hz, 2H), 6.93 (d, J = 9.0 Hz, 2H), 3.73 (s, 3H) ppm. 13C{1H}
NMR (100 MHz, DMSO-d6): δ 155.0, 152.8, 147.6, 138.3, 132.6,
126.5, 125.2, 120.6, 114.1, 55.2 ppm. HRMS (HESI/Orbitrap) m/z:
+
Orbitrap) m/z: [M + H]+ calcd for C13H11FN5 , 256.0993; found,
+
[M + H]+ calcd for C14H13N6O3 , 313.1044; found, 313.1057.
256.0993.
N-Phenyl-1-(3-(trifluoromethyl)phenyl)-1H-tetrazol-5-amine
(7g). Following the general procedure A, compound 7g was obtained
after dry-flash column chromatography (SiO2: Hex/EtOAc = 9/1) as
a pale yellow powder (155 mg, 86%) from 5a (100 mg, 0.620 mmol)
and 6d (82 μL, 0.59 mmol); mp 103−106 °C. IR (ATR): 3254, 3101,
3058, 1620, 1591, 1533, 486, 1463, 1339, 1320, 1292, 1150, 1112,
1-(4-Fluorophenyl)-N-phenyl-1H-tetrazol-5-amine (7l). Follow-
ing the general procedure A, compound 7l was obtained after dry-
flash column chromatography (SiO2: Hex/EtOAc = 8/2) as an off-
white powder (118 mg, 87%) from 5f (100 mg, 0.559 mmol) and 6b
(55 μL, 0.53 mmol); mp 145−147 °C. IR (ATR): 3260, 3207, 3125,
3095, 3060, 3010, 2940, 2866, 1620, 1575, 1539, 1508, 1462, 1422,
1322, 1228, 1184, 1157, 1127, 1094, 1039, 1014, 994, 889, 841, 807,
751, 693, 632, 597, 536, 501 cm−1. 1H NMR (400 MHz, DMSO-d6):
δ 9.29 (s, 1H), 7.80−7.70 (m, 2H), 7.66−7.58 (m, 2H), 7.55−7.47
(m, 2H), 7.36−7.28 (m, 2H), 7.03−6.97 (m, 1H) ppm. 13C{1H}
NMR (100 MHz, DMSO-d6): δ 162.7 (d, J = 246 Hz), 152.5, 139.8,
129.4 (d, J = 3 Hz), 128.8, 128.6 (d, J = 9 Hz), 122.1, 118.2, 116.9 (d,
J = 23 Hz) ppm. HRMS (HESI/Orbitrap) m/z: [M + H]+ calcd for
1
1094, 1068, 805, 766, 697 cm−1. H NMR (400 MHz, DMSO-d6): δ
9.68 (s, 1H), 8.05 (s, 1H), 7.96−7.92 (m, 1H), 7.73−7.61 (m, 5H),
7.59−7.54 (m, 1H), 7.36−7.32 (m, 1H) ppm. 13C{1H} NMR (100
MHz, DMSO-d6): δ 152.0, 140.7, 132.9, 130.3, 130.1, 130.0, 129.6 (q,
J = 31 Hz), 125.8, 124.2 (q, J = 270 Hz), 121.8 (q, J = 1 Hz), 118.3
(q, J = 4 Hz), 114.4 (q, J = 4 Hz) ppm. HRMS (HESI/Orbitrap) m/
+
z: [M + H]+ calcd for C14H11F3N5 , 306.0961; found, 306.0976.
+
N-Phenyl-1-(3-(trifluoromethyl)phenyl)-1H-tetrazol-5-amine
(7h). Following the general procedure A, compound 7h was obtained
after dry-flash column chromatography (SiO2: Hex/EtOAc = 9/1) as
an orange powder (211 mg, 63%) from 5d (250 mg, 1.17 mmol) and
6b (115 μL, 1.10 mmol); mp 79−81 °C. IR (ATR): 3192, 3081,
3038, 2997, 1613, 1572, 1532, 1495, 1470, 1451, 1334, 1313, 1250,
C13H11FN5 , 256.0993; found, 256.0994.
N-(3-Chlorophenyl)-1-phenyl-1H-tetrazol-5-amine (7m). Follow-
ing the general procedure A, compound 7m was obtained after dry-
flash column chromatography (SiO2: Hex/EtOAc = 8/2) as an off-
yellow powder (60 mg, 88%) from 5a (42 mg, 0.26 mmol) and 6g (29
μL, 0.25 mmol); mp 114−117 °C. IR (ATR): 3233, 3160, 3072,
3033, 2974, 1612, 1595, 1566, 1527, 1496, 1479, 1455, 1091, 1072,
1020, 909, 872, 772, 766, 687 cm−1. 1H NMR (400 MHz, DMSO-d6):
δ 9.56 (s, 1H), 7.83−7.78 (m, 1H), 7.71−7.61 (m, 5H), 7.60−7.55
(m, 1H), 7.38−7.32 (m, 1H), 7.08−7.03 (m, 1H) ppm. 13C{1H}
NMR (100 MHz, DMSO-d6): δ 151.9, 141.4, 133.2, 132.9, 130.5,
130.2, 130.0, 125.7, 121.6, 117.6, 116.6 ppm. HRMS (HESI/
1
1161, 1135, 1098, 1073, 85, 749, 699 cm−1. H NMR (400 MHz,
DMSO-d6): δ 9.45 (s, 1H), 8.13 (s, 1H), 8.04−7.98 (m, 2H), 7.92−
7.87 (m, 1H), 7.63−7.58 (m, 2H), 7.36−7.30 (m, 2H), 7.04−6.99
(m, 1H) ppm. 13C{1H} NMR (100 MHz, DMSO-d6): δ 152.5, 139.7,
133.8, 131.3, 130.5 (q, J = 32 Hz), 130.1, 128.9, 126.9 (q, J = 4 Hz),
123.6 (q, J = 217 Hz), 123.1 (q, J = 4 Hz), 122.3, 118.4 ppm. HRMS
+
(HESI/Orbitrap) m/z: [M + H]+ calcd for C14H11F3N5 , 306.0961;
+
Orbitrap) m/z: [M + H]+ calcd for C13H11ClN5 , 272.0698; found,
found, 306.0974.
272.0706.
N-(3-Fluorophenyl)-1-phenyl-1H-tetrazol-5-amine (7i). Follow-
ing the general procedure A, compound 7i was obtained after dry-
flash column chromatography (SiO2: Hex/EtOAc = 8/2) as an off-
white powder (121 mg, 91%) from 5a (90 mg, 0.56 mmol) and 6e
(58 μL, 0.52 mmol); mp 152−154 °C. IR (ATR): 3169, 3075, 2999,
2922, 1610, 1573, 1530, 1492, 1453, 1402, 1326, 1269, 1248, 1171,
1148, 1121, 1092, 1073, 1046, 1021, 992, 963, 924, 864, 824, 768,
727, 686, 631, 535 cm−1. 1H NMR (400 MHz, DMSO-d6): δ 9.59 (s,
1H), 7.76−7.61 (m, 5H), 7.61−7.52 (m, 1H), 7.48−7.40 (m, 1H),
7.39−7.30 (m, 1H), 6.89−6.77 (m, 1H) ppm. 13C{1H} NMR (100
MHz, DMSO-d6): δ 162.4 (d, J = 240 Hz), 152.0, 141.7 (d, J = 11
Hz), 132.9, 130.4 (d, J = 10 Hz), 130.2, 130.0, 125.7, 114.1 (d, J = 2
Hz), 108.4 (d, J = 21 Hz), 105.0 (d, J = 27 Hz) ppm. HRMS (HESI/
1-(3-Chlorophenyl)-N-phenyl-1H-tetrazol-5-amine (7n). Follow-
ing the general procedure A, compound 7n was obtained after dry-
flash column chromatography (SiO2: Hex/EtOAc = 8/2) as an off-
yellow powder (58 mg, 85%) from 5g (51 mg, 0.26 mmol) and 6b
(26 μL, 0.25 mmol); mp 96−98 °C. IR (ATR): 3192, 3114, 3078,
3035, 2992, 2919, 1615, 1572, 1531, 1499, 1482, 1436, 1253, 1100,
1
1086, 787, 768, 749, 693 cm−1. H NMR (400 MHz, DMSO-d6): δ
9.39 (s, 1H), 7.86 (s, 1H), 7.75−7.65 (m, 3H), 7.65−7.59 (m, 2H),
7.37−7.29 (m, 2H), 7.05−6.99 (m, 1H) ppm. 13C{1H} NMR (100
MHz, DMSO-d6): δ 152.4, 139.7, 134.2, 134.0, 131.5, 130.2, 128.8,
126.0, 124.8, 122.2, 118.4 ppm. HRMS (HESI/Orbitrap) m/z: [M +
+
H]+ calcd for C13H11ClN5 , 272.0698; found, 272.0709.
N-(1-Phenyl-1H-tetrazol-5-yl)pyridin-3-amine (7o). Following the
general procedure A, compound 7o was obtained after dry-flash
column chromatography (SiO2: Hex/EtOAc = 6/4) as a pale yellow
powder (50 mg, 84%) from 5a (42 mg, 0.26 mmol) and 6h (24 μL,
0.25 mmol); mp 125−126 °C. IR (ATR): 3258, 3051, 2962, 1611,
+
Orbitrap) m/z: [M + H]+ calcd for C13H11FN5 , 256.0993; found,
256.0993.
1-(3-Fluorophenyl)-N-phenyl-1H-tetrazol-5-amine (7j). Follow-
ing the general procedure A, compound 7j was obtained after dry-
flash column chromatography (SiO2: Hex/EtOAc = 8/2) as an off-
white powder (130 mg, 96%) from 5e (100 mg, 0.560 mmol) and 6b
1
1570, 1532, 1499, 1486 cm−1. H NMR (400 MHz, DMSO-d6): δ
9.58 (s, 1H), 8.82−8.78 (m, 1H), 8.25−8.20 (m, 1H), 8.13−8.08 (m,
4800
J. Org. Chem. 2021, 86, 4794−4803