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Organic & Biomolecular Chemistry
C, 70.09; H, 10.78; N, 9.08; Found: C, 70.34; H, 10.42;
N, 9.05.
Compound 3e. White solid (81.6 mg, 68% yield): mp
174–176 °C. H NMR (500 MHz, CDCl3) δ 8.81 (s, 1H), 8.52 (d,
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2-((Diphenylphosphino)methyl)pyridine L10. Compound L10
was prepared as a white solid (4.2 g, 56% yield) according to
the literature.28 1H NMR (500 MHz, CDCl3, δ) 8.50 (d, J =
5.5 Hz, 1H), 7.48 (d, J = 1.8 Hz, 1H), 7.44–7.32 (m, 10H), 7.06
(t, J = 7.0 Hz, 1H), 6.97 (d, J = 8.7 Hz, 1H), 3.64 (s, 2H);
31P NMR (202 MHz, CDCl3) δ −10.34.
J = 4.7 Hz, 1H), 8.24 (d, J = 8.2 Hz, 1H), 7.94 (td, J = 8.0, 1.7 Hz,
1H), 7.82 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 8.4 Hz, 2H), 7.37 (dd,
J = 7.3, 4.9 Hz, 1H). 13C NMR (126 MHz, CDCl3) δ 149.0, 148.6,
147.0, 139.2, 133.8, 132.0, 131.8, 129.2, 127.4, 123.7, 122.4,
116.9, 113.8. ESI-MS calcd for C13H9BrN4: 300.00; Found:
[M + H]+ 301.53. HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C13H9BrN4 301.0089; Found: 301.0087.
Representative procedure for the preparation of 1-(pyridin-
2-yl)-1,2,3-triazole derivatives 3a–3p (Table 4, entry 1, as an
Compound 3f. White solid (49.9 mg, 52% yield): mp
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example). Under a nitrogen atmosphere, a 25 mL Schlenk 108–111 °C. H NMR (500 MHz, CDCl3) δ 8.79 (s, 1H), 8.56 (s,
tube was charged with anhydrous toluene (0.80 mL), CuCl 1H), 8.27 (d, J = 6.8 Hz, 1H), 8.01–7.86 (m, 3H), 7.39 (s, 1H),
(2 mg, 0.02 mmol) and the ligand L9 (12.32 mg, 0.04 mmol). 7.17 (t, J = 8.6 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 148.1,
The mixture was stirred for 30 min at room temperature. Then 147.5, 138.2, 126.6, 125.4, 122.6, 115.5, 115.0, 114.8, 112.8,
tetrazolo[1,5-a]pyridine 2a (48 mg, 0.4 mmol), ferrocenylacety- 76.3, 76.0, 75.7, 31.3. Anal. Calcd for C13H9FN4: C, 64.99;
lene (101 mg, 0.48 mmol) and anhydrous toluene (0.80 mL) H, 3.78; N, 23.32; Found: C, 65.21; H, 3.52; N, 22.99. ESI-MS
were added into the Schlenk tube successively. Then the calcd for C13H9FN4: 240.08. Found: [M]+ 240.95.
Compound 3g. White solid (80.9 mg, 79% yield): mp
137–14 °C. H NMR (500 MHz, CDCl3) δ 8.82 (s, 1H), 8.52 (d,
mixture was stirred for 12 h at 120 °C and cooled. Removal of
the solvent yielded a residue, which was purified by flash
column chromatography (silica gel, CH2Cl2–EtOAc–hexane =
1 : 1 : 5) to give compound 3a as an orange solid (125.0 mg,
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J = 4.3 Hz, 1H), 8.23 (d, J = 8.2 Hz, 1H), 7.98–7.90 (m, 2H), 7.81
(d, J = 7.6 Hz, 1H), 7.42–7.35 (m, 2H), 7.33 (d, J = 8.0 Hz, 1H).
13C NMR (126 MHz, CDCl3) δ 149.0, 148.6, 146.7, 139.2, 134.9,
132.0, 130.2, 128.4, 125.9, 123.9, 123.7, 117.2, 113.8. Anal.
Calcd for C13H9ClN4: C, 60.83; H, 3.53; N, 21.83; Found:
C, 60.73; H, 3.23; N, 21.43. ESI-MS calcd for C13H9ClN4:
256.05. Found: [M + H]+ 257.11.
Compound 3h. White solid (72.3 mg, 81% yield): mp
132–134 °C. 1H NMR (500 MHz, CDCl3) δ 9.18 (s, 1H), 8.66
(s, 1H), 8.55 (d, J = 3.8 Hz, 1H), 8.25 (d, J = 7.7 Hz, 2H), 7.94
(t, J = 7.6 Hz, 1H), 7.82 (t, J = 7.2 Hz, 1H), 7.41–7.32 (m, 1H),
7.27 (s, 1H). 13C NMR (126 MHz, CDCl3) δ 150.0, 149.7, 149.1,
148.8, 148.6, 139.1, 136.9, 123.7, 123.1, 120.5, 119.4, 113.9.
ESI-MS calcd for C12H9N5: 223.09. Found: [M + H] 224.07.
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C12H9N5 224.0936;
Found: 224.0928.
Compound 3i. White solid (70.2 mg, 77% yield): mp
129–134 °C. 1H NMR (500 MHz, CDCl3) δ 8.71 (s, 1H), 8.51
(d, J = 4.2 Hz, 1H), 8.22 (d, J = 8.2 Hz, 1H), 7.92 (dd, J = 11.2,
4.4 Hz, 1H), 7.50 (d, J = 3.2 Hz, 1H), 7.42–7.31 (m, 2H),
7.17–7.05 (m, 1H). 13C NMR (126 MHz, CDCl3) δ 149.0, 148.6,
143.3, 139.2, 132.5, 127.8, 125.5, 124.7, 123.7, 116.2, 113.9.
ESI-MS calcd for C11H8N4S: 228.05. Found: [M + H]+ 229.11.
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C11H8N4S 229.0548;
Found: 229.0546.
Compound 3j. White solid (41.8 mg, 55% yield): mp
69–71 °C. 1H NMR (500 MHz, CDCl3) δ 8.47 (dd, J = 28.0,
10.2 Hz, 2H), 8.27–8.08 (m, 1H), 7.92 (s, 1H), 7.35 (s, 1H), 4.04
(s, 2H), 3.07 (s, 2H), 2.60 (s, 1H). 13C NMR (126 MHz, CDCl3)
δ 149.3, 148.5, 139.1, 127.4, 123.5, 122.9, 119.4, 113.7, 61.5,
31.0. ESI-MS calcd for C9H10N4O: 190.09. Found: [M + H]+
191.21. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C9H10N4ONa
213.0752; Found: 213.0748.
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95% yield): mp 235–238 °C. H NMR (500 MHz, CDCl3) δ 8.51
(d, J = 20.3 Hz, 2H), 8.24 (d, J = 8.2 Hz, 1H), 8.02–7.79 (m, 1H),
7.36 (dd, J = 6.8, 5.2 Hz, 1H), 4.85 (s, 2H), 4.37 (s, 2H), 4.13 (s,
5H); 13C NMR (126 MHz, CDCl3) δ 149.2, 148.5, 147.5, 139.1,
123.4, 115.8, 113.8, 77.3, 77.0, 76.8, 69.7, 68.9, 66.9. Anal.
Calcd for C17H14FeN4: C, 61.84; H, 4.27; N, 16.97; Found: C,
61.75; H, 4.34; N, 16.89. ESI-MS calcd for C17H14FeN4: 330.06,
Found: [M]+ 330.8.
Compound 3b.4e White solid (84.4 mg, 95% yield): mp
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129–131 °C. H NMR (500 MHz, CDCl3) δ 8.82 (s, 1H), 8.53 (d,
J = 4.3 Hz, 1H), 8.26 (d, J = 8.2 Hz, 1H), 8.01–7.91 (m, 3H), 7.47
(t, J = 7.7 Hz, 2H), 7.37 (dd, J = 13.6, 6.2 Hz, 2H). 13C NMR
(126 MHz, CDCl3) δ 149.2, 148.6, 139.2, 130.2, 128.9, 128.5,
125.9, 123.6, 116.8, 113.9, 77.3, 77.0, 76.8, 32.3. Anal. Calcd for
C13H10N4: C, 70.26; H, 4.54; N, 25.21; Found: C, 69.96; H, 4.35;
N, 25.01. ESI-MS calcd for C13H10N4: 222.09; Found: [M + H]+
223.03.
Compound 3c. White solid (91.6 mg, 97% yield): mp
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119–121 °C. H NMR (500 MHz, CDCl3) δ 8.79 (d, J = 14.9 Hz,
1H), 8.54 (s, 1H), 8.26 (d, J = 7.8 Hz, 1H), 7.94 (t, J = 7.8 Hz,
1H), 7.83 (t, J = 10.5 Hz, 2H), 7.37 (d, J = 5.5 Hz, 1H), 7.32–7.22
(m, 2H), 2.41 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 149.2,
148.5, 139.1, 138.4, 129.6, 127.4, 125.8, 123.5, 123.0, 116.4,
113.9, 21.4. Anal. Calcd for C14H12N4: C, 71.17; H, 5.12;
N, 23.71; Found: C, 70.97; H, 5.51; N, 23.52. ESI-MS calcd for
C14H12N4: 236.11; Found: [M]+ 236.94.
Compound 3d. White solid (98.8 mg, 98% yield): mp
106–109 °C. 1H NMR (500 MHz, CDCl3) δ 8.74 (s, 1H), 8.55
(s, 1H), 8.26 (d, J = 6.9 Hz, 1H), 7.94 (t, J = 7.7 Hz, 1H), 7.88 (d,
J = 8.6 Hz, 2H), 7.37 (s, 1H), 7.01 (d, J = 8.6 Hz, 2H), 3.87 (s,
3H). 13C NMR (126 MHz, CDCl3) δ 160.0, 148.7, 139.3, 127.4,
123.4, 123.0, 116.0, 114.5, 114.0, 55.5. Anal. Calcd for
C14H12N4O: C, 66.65; H, 4.79; N, 22.21; Found: C, 66.83;
H, 4.59; N, 22.05. ESI-MS calcd for C14H12N4O: 252.10; Found:
[M]+ 252.89.
Compound 3k. Colorless liquid (43.5 mg, 49% yield).
1H NMR (500 MHz, CDCl3) δ 8.46 (d, J = 3.4 Hz, 1H), 8.35
(s, 1H), 8.15 (d, J = 8.0 Hz, 1H), 7.88 (t, J = 7.4 Hz, 1H),
7.37–7.27 (m, 1H), 3.60 (t, J = 6.2 Hz, 2H), 2.97 (t, J = 7.1 Hz,
5960 | Org. Biomol. Chem., 2014, 12, 5954–5963
This journal is © The Royal Society of Chemistry 2014