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DOI: 10.1055/s-2007-990965
Useful Preparation of 6-Phenyl-2,2′-Bipyridine Ligands Bearing Di-n-butylaminophenyl or Gallate Derivatives Substituted in the 3- or 4-Positions
Publication History
Publication Date:
08 November 2007 (online)
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Abstract
A simple protocol for the efficient preparation of substituted 6-phenyl-2,2′-bipyridine derivatives is described. A reverse type of Diels-Alder reaction between a 6-phenyl-2-pyridyl-1,3,4-triazine and 4-N,N-di-n-butylaminophenyl- or gallate-ethynyl derivatives at high temperature provide a mixture of two products easily separable by column chromatography. A variety of ligands suitable for the synthesis of cyclometalated platinum complexes have been produced. Additional substitution of the Pt-Cl by various donor-acceptor ethynyl fragments is feasible by mean of copper(I) catalysis.
Key words
triazine - retro-Diels-Alder - gallate - fluorescence - platinum
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References and Notes
3,4-Bis(
N
,
N
-dibutyl-4-aminophenyl)-6-phenyl-2,2′-bipyridine(4)
A Schlenk tube was charged with 6-phenyl-2-pyridyl-1,3,4-triazine (1, 125 mg, 0.53 mmol), N,N-dibutyl-4-{2-[4 (dibutylamino)phenyl]ethynyl}benzenamine (230 mg, 0.53 mmol) and o-dichlorobenzene (1 mL). The mixture was argon-degassed via at least three freeze-pump-thaw cycles, heated to 190 °C and finally stirred in the dark for 1-3 d. The solvent was removed under high vacuum. The residue was treated with H2O and extracted with CH2Cl2. The organic extracts were washed with H2O, then with sat. brine and filtered through cotton wool. The solvent was removed by rotary evaporation, and the residue was purified by chromatography on aluminium oxide eluting with CH2Cl2-PE (v/v 0:1 to 50:50) to afford 194 mg (57%) of 4 as a white to light pink powder. 1H NMR (400 MHz, CDCl3): δ = 8.59 (d, 1 H, 3
J = 4.5 Hz), 8.11 (d, 2 H, 3
J = 7.0 Hz), 7.80 (s, 1 H), 7.49-7.35 (m, 4 H), 7.19 (d, 1 H, 3
J = 8.0 Hz), 7.09 (ddd, 1 H, J = 7.5, 4.8, 1.3 Hz), 6.78 (ABsys, 4 H, J
AB = 9.0 Hz, ν0δ = 220.6 Hz), 6.55 (ABsys, 4 H, J
AB = 8.8 Hz, ν0δ = 144.5 Hz), 3.24 (t, 4 H, 3
J = 7.5 Hz), 3.17 (t, 4 H, 3
J = 7.5 Hz), 1.59-1.44 (m, 8 H), 1.38-1.24 (m, 8 H), 0.95 (t, 6 H, 3
J = 7.3 Hz), 0.92 (t, 6 H, 3
J = 7.5 Hz). 13C NMR (100 MHz, CDCl3): δ = 160.2, 157.7, 155.3, 150.5, 149.0, 147.5, 146.9, 139.9, 135.3, 133.3, 132.2, 130.7, 128.6, 128.5, 127.3, 126.3, 125.2, 124.7, 121.6, 121.5, 111.7, 111.1, 50.8, 50.7, 29.5, 29.4, 20.5, 20.4, 14.2, 14.1. UV/Vis (CH2Cl2): λ nm (ε, M-1 cm-1) = 355 (sh, 19200), 331 (2860), 263 (30600). IR (KBr): ν = 3039 (w), 2955 (m), 2929 (m), 2870 (m), 1605 (s), 1517 (s), 1463 (m), 1364 (s), 1285 (m), 1198 (s), 1095 (m), 818 (s) cm-1. MS-FAB+: m/z (nature of the peak, relative intensity) = 639.3 (100) [M + H]+. Anal. Calcd for C44H54N4: C, 82.71; H, 8.52; N, 8.77. Found: C, 82.54; H, 8.29; N, 8.47.
Crystal data for 4 at 293 K: C44H54N4, M = 638.91, monoclinic, space group P21/c, a = 15.161(5) Å, b = 25.720(5) Å, c = 10.503(5) Å, α = 90.000(5)°, β = 107.245(5)°, γ = 90.000(5)° V = 3911.44(10) Å3, Z = 4, λ = 0.71069 Å, D c = 1.085 g cm-3, µ = 0.063 mm-1, 23064 reflections collected with θ £ 18.91°, 3085 unique, R(int) = 0.1214, and 1926 observed reflections [I ³ 2σ(I)], 433 parameters, R1 = 0.0830, wR2 = 0.2397 refined on F 2. CCDC 649879.
22Crystal data for 7 at 293 K: C30H32ClN3Pt, M = 665.13, triclinic, space group P-1, a = 9.147(1) Å, b = 9.979(1) Å, c = 15.290(2) Å, α = 80.500(3)°, β = 80.922(2)°, γ = 73.057(3)°, V = 1307.8(3) Å3, Z = 2, λ = 0.71069 Å, D c = 1.689 g cm-3, µ = 5.49 mm-1, 15122 reflections collected with θ £ 27.61°, 5869 unique, R(int) = 0.0501, and 4993 observed reflections [I ³ 2σ(I)], 354 parameters, R1 = 0.0383, wR2 = 0.0919 refined on F 2. CCDC 649883.