E. Obijalska et al. / Polyhedron 30 (2011) 1339–1348
1347
for C13H12N4O: C, 64.99; H, 5.03; N, 23.32. Found: C, 64.81; H, 5.00;
N, 23.26%.
1H), 7.72–7.63 (m, 1H), 7.51 (t, J = 4.8 Hz, 1H), 7.41 (ddd,
J1 = 11.0 Hz, J2 = 8.4 Hz, J3 = 1.0 Hz, 1H), 7.34 (t, J = 8.0 Hz,
1H) ppm. Anal. Calc. for C10H7FN4: C, 59.40; H, 3.49; N, 27.71.
Found: C, 59.52; H, 3.50; N, 27.66%.
5.4. 2-(6-Metoxy-3-pyridazinyl)-2H-benzotriazole (9)
CH2Cl2 with increasing amounts of MeCN (0–15%) was used as
an eluent. Yield: 76 mg (33%); colorless crystals (iso-octane/
CH2Cl2): mp 174–175 °C; 1H NMR (CDCl3) d 8.42 (d, J = 9.4 Hz,
1H), 8.01–7.98 (m, 2H), 7.51–7.46 (m, 2H), 7.24 (d, J = 9.5 Hz,
5.6.3. 3-(2-Fluorophenylazo)-6-methoxypyridazine (16)
Yield 67%; red crystals (cyclohexane/CH2Cl2): mp 107–108 °C;
1H NMR (CDCl3) d 7.96 (d, J = 9.3 Hz, 1H), 7.95–7.92 (m, 1H),
7.56–7.49 (m, 1H), 7.31–7.22 (m, 2H), 7.11 (d, J = 9.3 Hz, 1H),
4.25 (s, 3H) ppm. Anal. Calc. for C11H9FN4O: C, 56.90; H, 3.91; N,
24.13. Found: C, 56.77; H, 3.73; N, 24.02%.
1H), 4.26 (s, 3H) ppm; IR (KBr)
748 cmꢀ1
UV, kmax (log
(4.31) nm; GC–MS (EI) m/z 227 (M+, 100). Anal. Calc. for
11H9N5O: C, 58.15; H, 3.99; N, 30.82. Found: C, 58.42; H, 3.95;
N, 30.56%.
v
3069, 1402, 1308, 1283, 1005,
e) 304 (4.36) 236sh (4.10), 222
;
C
5.7. 1-(2-Pyrimidinyl)-1H-benzotriazole (12) [24]
Following the general procedure, compound 12 was isolated in
56% yield (110 mg) using CH2Cl2 as the eluent. Colorless crystals,
(iso-octane/CH2Cl2): mp 169–171 °C (lit. [24] 164–165 °C); 1H
NMR (CDCl3) d 8.97 (d, J = 4.7 Hz, 2H), 8.62 (d, J = 8.4 Hz, 1H),
8.20 (d, J = 8.2 Hz, 1H), 7.67 (t, J = 7.5 Hz, 1H), 7.51 (t, J = 7.8 Hz,
5.5. [(2-(2-Pyridinyl)-2H-benzotriazole)(bpy)2Ru]2+[PF6]2 (7a-Ru)
2ꢀ
2-(2-Pyridinyl)-2H-benzotriazole (7a, 68 mg, 0.3 mmol) and
(bpy)2RuCl2ꢁH2O[53] (150 mg, 0.29 mmol, 1H NMR (DMSO-d6) d
9.96 (d, J = 5.37 Hz, 1H), 8.63 (d, J = 8.1 Hz, 1H), 8.47 (d, J = 7.8 Hz,
1H), 8.06 (t, J = 7.2 Hz, 1H), 7.76 (t, J = 6.2 Hz, 1H), 7.67 (t,
J = 8.1 Hz, 1H), 7.50 (d, J = 5.5 Hz, 1H) 7.09 (t, J = 6.8 Hz, 1H) ppm)
in a 3:1 mixture of EtOH–H2O (20 ml) were refluxed for 3 h. After
cooling, solvents were evaporated, and the residue was dissolved
in minimum amounts of water and filtered. An aqueous solution
of [NH4]+[PF6]ꢀ was added, the resulting precipitation was filtered,
dissolved in CH2Cl2, and the solution was dried (Na2SO4). The crude
product was purified by column chromatography (Al2O3, CH2Cl2–
MeOH, 9:1) to give 240 mg (92% yield) of red crystals. The product
was double recrystallized by dissolving in a small amounts of
MeCN and overlaying with toluene: mp > 260 °C; 1H NMR (CD3CN)
d 8.64 (d, J = 8.2 Hz, 1H), 8.54–8.49 (m, 3H), 8.46 (d, J = 8.2 Hz, 1H),
8.25 (td, J1 = 8.0 Hz, J2 = 1.4 Hz, 1H), 8.17 (td, J1 = 7.9 Hz, J2 = 1.4 Hz,
1H), 8.11–8.00 (m, 4H), 7.90 (d, J = 5.6 Hz, 1H), 7.80 (d, J = 5.5 Hz,
1H), 7.73 (d, J = 5.5 Hz, 2H), 7.67 (d, J = 5.6 Hz, 1H), 7.60 (t,
J = 8.0 Hz, 1H), 7.54–7.29 (m, 6H), 6.02 (d, J = 8.8 Hz, 1H) ppm;
1H), 7.40 (t, J = 4.7 Hz, 1H) ppm; IR (KBr)
v 1569, 1461, 1430,
1293, 1054, 742 cmꢀ1; UV, kmax (log
e) 298 (4.00), 257 (4.09), 236
(4.27), 227sh (4.25) nm; MS (FAB), m/z 198 (MH+, 100); HRMS,
m/z calcd for C10H8N5: 198.0780; found: 198.0777.
5.8. 2-(6-Keto-1-methyl-3-pyridazinyl)-2H-benzotriazole (17)
Obtained in 51% yield (116 mg) as the second, more polar frac-
tion during isolation of 9. Yellow crystals (MeOH/CH2Cl2):
mp > 260 °C; 1H NMR (CDCl3) d 8.37 (d, J = 9.9 Hz, 1H), 7.99–7.94
(m, 2H), 7.51–7.45 (m, 2H), 7.21 (d, J = 9.9 Hz, 1H), 3.97 (s, 3H)
ppm; IR (KBr),
(log
v
1670 (C@O), 1597, 1264, 962, 758 cmꢀ1; UV, kmax
e
) 299 (4.29), 2.34 (4.36), 227 (2.33) nm; GC–MS (EI), m/z 227
(M+, 100). Anal. Calc. for C11H9N5O: C, 58.15; H, 3.99; N, 30.82.
Found: C, 58.07; H, 3.98; N, 30.66.
Acknowledgements
UV, kmax (log e) 461sh, 434 (4.10), 339 (4.25), 306sh, 285 (4.81),
243 (4.49) nm. Anal. Calc. for C31H24N8RuP2F12ꢁMeCN: C, 42.14; H,
We thank to Mr. Bryan Ringstrand for help with preparing
single crystal of 7a-Ru for XRD analysis. Financial support for
this work was received from the Petroleum Research Funds
(PRF-47243-AC4) and NSF OISE (0532040).
2.89; N, 13.40. Found: C, 42.21; H, 2.74; N, 13.56%.
5.6. Preparation of 2-(2-Halophenylazo)azines 10 and 16. A general
procedure [27]
Appendix A. Supplementary data
Appropriate aminoazine (2-aminopyridyne, aminopyrazine, 2-
aminopyrimidine, or 3-amino-6-methoxypyridazine, 4.0 mmol)
was dissolved in toluene (5.0 ml) and 50% aqueous solution of
NaOH (3.4 ml) and 2-halonitrozobenzene (4.5 mmol) were added.
The mixture was vigorously stirred with a mechanical stirrer for
25 min at 50 °C. After cooling, water was added, and the mixture
was extracted with CH2Cl2. Extracts were dried (Na2SO4), and sol-
vents were evaporated. The residue was purified by column chro-
matography (silica gel) using hexane with increasing amounts of
CH2Cl2 (0–100%) as the eluent followed by crystallization from
appropriate solvent.
CCDC 785246 contains the supplementary crystallographic data
for 7a-Ru. These data can be obtained free of charge via http://
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data associated with this article can be found, in
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Yield 62%; red crystals (hexanes): mp 68–69 °C; 1H NMR
(CDCl3) d 9.00 (d, J = 4.8 Hz, 2H), 7.94 (t, J = 7.7 Hz, 1H), 7.63–7.56
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