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A.M. Prokhorov et al. / Journal of Organometallic Chemistry 693 (2008) 1886–1894
Complex 4: Dark-green crystals. Yield 70%. Anal. Calc
for C17H10N3BrCl2Cu (472.66): C, 43.20; H, 2.56; N, 16.91.
Found: C, 43.41; H, 2.32; N, 16.99%.
Complex 14: Dark-green crystals. Yield 65%. Anal.
Calc. for C14H11ClCuN4O2 (366.26): C, 45.91; H, 3.03;
N, 15.30. Found: C, 45.71; H, 3.05; N, 15.00%.
Complex 19: Dark-green crystals. Yield 80%. Anal.
Calc. for C44H30N8O2Cl2Cu2 (900.74): C, 58.67; H, 3.36;
N, 12.44. Found: C, 58.51; H, 3.32; N, 12.27%
the residue was treated with acetonitrile (5 mL), and yellow
solid was filtered off. The product was recrystallized from
toluene to give phenacyltriazine 18H. Yield 45%. M.p.:
156 °C. 1H NMR (CDCl3), d: 6.25 (s, 1H, COCH),
7.48–7.80 (m, 11H, Haromatic + H-50), 8.14 (m, 1H, H-40),
8.54 (m, 1H, H-30), 8.95 (m, 1H, H-60), 15.39 (br.s, 1H,
NH). Anal. Calc. for C22H16N4O (352.38): C, 74.98; H,
4.58; N, 15.90. Found: C, 74.79; H, 4.47; N, 15.86%.
4.6. Synthesis of complex 17
4.2. Synthesis of complex 8
Solution of ligand 15 (50 mg, 0.15 mmol) in acetonitrile
(30 mL) was added to a solution of CuCl2 2H2O (26 mg,
Solution of ligand 1a (39 mg, 0.15 mmol) in methanol
(15 mL) was added to solution of copper chloride dihy-
drate (26 mg, 0.15 mmol) in methanol (15 mL). Resulting
mixture was stirred under reflux for 1 day to give green
solution. The solution was cooled down and condensed
slowly for some days. Resulting green crystals were filtered
off. Yield 70%. Anal. Calc. for C72H62Cl8Cu4N12O5
(1713.10): C, 50.48; H, 3.65; N, 9.81. Found: C, 50.60; H,
3.41; N, 9.80%.
*
0.15 mmol) in acetonitrile (30 mL). The resulting dark
brown solution was kept for 3 days at r.t. Appeared
dark-green crystals were filtered off. Yield 88%. Anal. Calc.
for C24H16Cl2CuN2 (466.86): C, 61.75; H, 3.45; N, 6.00.
Found: C, 61.52; H, 3.62; N, 6.28%.
4.7. Synthesis of 3,6-diphenyl-5-phenylethynyl-1,2,4-triazine
(21)
4.3. Synthesis of complex 6
Solution of lithium phenylacetylide, prepared by addi-
tion of 1.6 M butyllithium in hexane (0.66 mL, 1.05 mmol)
to solution of phenylacetylene (0.11 mL, 1 mmol) in 10 ml
of THF, was added with stirring to solution of 1,2,4-tri-
azine 4-oxide 22 (250 mg, 1 mmol) in THF (10 ml) at
ꢁ40 °C under argon, and the mixture was kept at this
temperature for 20 min. Acetic anhydride (0.1 mL,
1.05 mmol) was added at the same temperature, and the
reactional mixture was allowed to warm up to room
temperature. Then the solvent was removed under reduced
pressure, the residue was dissolved in chloroform and
phenylethynyltriazine 21 was isolated by column chroma-
tography (silica gel, CH2Cl2). Analytical sample was
recrystallized from acetonitrile. Yield, 85%. M.p. 175 °C
(from acetonitrile). 1H NMR (CDCl3), d: 7.38–7.58 (m,
11H), 8.17 (m, 2H), 8.63 (m, 2H). 13C NMR (CDCl3), d:
86.38, 99.57, 120.74, 128.37, 128.64, 128.85, 129.29,
130.38, 130.56, 131.70, 132.53, 134.09, 134.38, 141.85,
156.62, 161.39. HRMS (EI): C23H15N3 requires M+,
333.1266, found 333.1254.
Solution of ligand 1a (39 mg, 0.15 mmol) and ethanol-
amine (0.30 mmol) in boiling acetonitrile (15 mL) was
added to solution of copper chloride dihydrate (51 mg,
0.30 mmol) in acetonitrile (15 mL) at 80 °C. Green precip-
itate was formed. The mixture was stirred under reflux for
1 hour to give dark green solution. The solution was cooled
down and condensed slowly for some days. Resulting dark-
green crystals were filtered off. Yield 65%. Anal. Calc. for
C40H44Cl5Cu3N8O4 (1068.70): C, 44.95; H, 4.15; N,
10.48. Found: C, 44.99; H, 4.11; N, 10.20%.
4.4. Synthesis of complexes 10 and 12
Solution of ligand 1a or 2(0.15 mmol) in hot methanol
(15 mL) was added to solution of copper chloride dihy-
drate (26 mg, 0.15 mmol) in water (30 mL). Resulting mix-
ture was stirred under reflux for 1 day to give blue solution.
The solution was condensed in vacuo in half and then
cooled down. Some days later appeared dark-blue crystals
were filtered off.
Complex 10: Dark-blue crystals. Yield 85%. Anal. Calc.
for C17H11ClCuN2O2 (374.27): C, 54.55; H, 2.96; N, 7.48.
Found: C, 54.60; H, 3.01; N, 7.20%.
Complex 12: Dark-blue crystals. Yield 90%. Anal. Calc.
for C40H30Cl2Cu2N4O4 (828.68): C, 57.97; H, 3.65; N, 6.76.
Found: C, 57.60; H, 3.42; N, 6.86%.
4.8. X-ray crystallography
Diffraction data of complexes 4, 6, 8, 10, 12, 14, 17 and
19 were collected on a Xcalibir 3 CCD diffractometer
with graphite monochromated Mo Ka radiation (k =
˚
0.71073 A). Details of X-ray crystallography for every
compound are given in the Table 1. Analytical numeric
absorption correction is applied using a multifaceted crys-
tal model. The structure is solved by direct method and
refined anisotropically with SHELX-97 program package
[28]. The coordinates of non-hydrogen atoms were refined
anisotropically, while hydrogen atoms were included in cal-
culations isotropically but not refined.
4.5. Synthesis of 5-phenacyl-6-phenyl-3-(2-pyridyl)-1,2,4-
triazine 18H
5-Ethynyl-1,2,4-triazine 16 (332 mg, 1 mmol) was dis-
solved in acetic acid (10 mL) with water (1 mL), and was
heated with reflux for 24 h. Then solvent was removed,