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DOI: 10.1055/s-2006-950266
Synthesis and Optical Properties of Starburst Carbazoles Based on 9-Phenylcarbazole Core
Publikationsverlauf
Publikationsdatum:
09. Oktober 2006 (online)
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Abstract
New well-defined starburst carbazole derivatives, which contain N-phenylcarbazole as the central core joining 9-hexylcarbazole or 9-phenylcarbazole as arms, are presented. All these compounds were obtained via Suzuki cross-coupling in moderate yields. Their structures were confirmed by 1H NMR, MALDI-TOF mass spectrometry and elementary analysis. Moreover, the fluorescence spectra showed that these compounds exhibited good blue fluorescence with the maximum wavelengths ranging from 410 nm to 430 nm.
Key words
carbazole - starburst - boronic acids - Suzuki cross-coupling - fluorescence
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References and Notes
Synthesis of Compounds 9 and 11; Typical Procedure
To a solution of the corresponding 3-bromocarbazole derivatives 6 or 7 (10 mmol) in anhyd THF (50 mL) was slowly added n-BuLi (2.5 M in hexane, 4.8 mL, 12.0 mmol) at -78 °C. At this temperature, the reaction mixture was stirred for 1 h before adding triisopropyl borate (3.5 mL, 15.0 mmol). The mixture was allowed to warm to r.t. for
15 h. It was quenched with HCl (2.0 M, 40 mL) and poured into a large amount of water. After extraction with Et2O (3 × 20 mL), the organic portions were washed with brine before drying over anhyd MgSO4 and the solvent was evaporated to afford the crude carbazoleboronic acids. The crude product was purified by column chromatography on a silica gel column, eluting with PE and EtOAc (2:1) to afford carbazoleboronic acids, which were then dried in vacuo at 35 °C.
Compound 9: 1H NMR (400 MHz, CDCl3): δ = 8.54 (s, 1 H), 8.34-8.38 (m, 2 H), 8.12 (d, J = 8.0 Hz, 1 H), 7.78-7.82 (m, 3 H), 7.60 (s, 1 H), 7.25-7.48 (m, 6 H), 4.34-4.39 (m, 4 H), 1.90-1.98 (m, 4 H), 1.20-1.46 (m, 12 H), 0.88-0.90 (m, 6 H).
Compound 11: 1H NMR (400 MHz, CDCl3): δ = 8.60 (s, 1 H), 8.36-8.40 (m, 2 H), 8.07-8.14 (m, 2 H), 7.80-7.86 (m, 2 H), 7.58-7.70 (m, 4 H), 7.28-7.50 (m, 12 H).
Synthesis of Starburst Compounds 12-15; General Procedure
To a degassed (N2) solution of 9-(4-bromophenyl)-3,6-dibromocarbazole (1; 1.0 g, 2.1 mmol) and Pd(PPh3)4 catalyst (0.5 g, 0.44 mmol, 7 mol% per C-Br bond) in toluene (30 mL), a solution of carbazoleboronic acid (9.45 mmol) in toluene (20 mL) and a 2 M aq K2CO3 solution (13 mL) were added via syringe. The reaction mixture was stirred at 80 °C for 48 h. After cooling, the product was extracted with CH2Cl2, washed with water and dried over MgSO4. The solvent was evaporated to afford the crude mixture. After column chromatography on silica gel, eluting with PE and CH2Cl2 (5:1), pure compounds 12-15 were obtained. All the compounds were fully characterized. The analytical and spectral data for these compounds follow:
Compound 12: 1H NMR (400 MHz, CDCl3): δ = 8.58 (s, 2 H), 8.46 (d, J = 7.6 Hz, 3 H), 8.21 (d, J = 7.6 Hz, 3 H), 8.01 (d, J = 7.4 Hz, 2 H), 7.78-7.88 (m, 6 H), 7.65 (d, J = 7.4 Hz, 2 H), 7.43-7.56 (m, 7 H), 7.25-7.30 (m, 6 H), 4.32-4.39 (m, 6 H), 1.89-1.92 (m, 6 H), 1.28-1.37 (m, 18 H), 0.87-0.91 (m, 9 H). Anal. Calcd for C72H70N4: C, 87.23; H, 7.12; N, 5.65. Found: C, 87.30; H, 7.27; N, 5.60. MS (MALDI-TOF): m/z [M+] calcd for C72H70N4: 991; found: 991.
Compound 13: 1H NMR (400 MHz, CDCl3): δ = 8.60 (s, 2 H), 8.52 (d, J = 7.6 Hz, 3 H), 8.26 (d, J = 7.6 Hz, 3 H), 8.02 (d, J = 7.4 Hz, 2 H), 7.76-7.86 (m, 6 H), 7.63-7.68 (m, 12 H), 7.44-7.57 (m, 12 H), 7.25-7.36 (m, 6 H). Anal. Calcd for C72H46N4: C, 89.41; H, 4.79; N, 5.79. Found: C, 89.23; H, 4.82; N, 5.43. MS (MALDI-TOF): m/z [M+] calcd for C72H46N4: 967; found: 967.
Compound 14: 1H NMR (400 MHz, CDCl3): δ = 8.63 (s, 2 H), 8.54-8.57 (m, 6 H), 8.45 (s, 3 H), 8.17-8.20 (m, 3 H), 8.04 (d, J = 7.4 Hz, 2 H), 7.79-7.90 (m, 10 H), 7.67 (d, J = 7.4 Hz, 2 H), 7.25-7.49 (m, 15 H), 7.20-7.23 (m, 6 H), 4.3-4.4 (m, 12 H), 1.82-1.97 (m, 12 H), 1.25-1.56 (m, 36 H), 0.84-0.92 (m, 18 H). Anal. Calcd for C126H127N7: C, 87.00; H, 7.36; N, 5.64. Found: C, 87.15; H, 7.13; N, 5.80. MS (MALDI-TOF): m/z [M+] calcd for C126H127N7: 1739; found: 1739.
Compound 15: 1H NMR (400 MHz, CDCl3): δ = 8.64 (s, 2 H), 8.58-8.62 (m, 6 H), 8.50 (s, 3 H), 8.22-8.23 (m, 3 H), 8.05 (d, J = 7.4 Hz, 2 H), 7.78-7.88 (m, 12 H), 7.39-7.67 (m, 42 H), 7.24-7.26 (m, 9 H). Anal. Calcd for C126H79N7: C, 89.49; H, 4.71; N, 5.80. Found: C, 89.32; H, 4.49; N, 5.94. MS (MALDI-TOF): m/z [M+] calcd for C126H79N7: 1691; found: 1691.