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Synlett 2014; 25(19): 2765-2768
DOI: 10.1055/s-0034-1379235
DOI: 10.1055/s-0034-1379235
letter
Novel Synthesis of 5-Substituted 5H-Benzo[b]carbazole-6,11-diones via Double Buchwald–Hartwig Reaction
Further Information
Publication History
Received: 23 July 2014
Accepted after revision: 11 September 2014
Publication Date:
16 October 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201419/lookinside/thumbnails/10.1055-s-0034-1379235-1.jpg)
Abstract
2-Bromo-3-(2-bromophenyl)naphthalene-1,4-dione was synthesized as a key precursor to obtain a number of functionalized benzo[b]carbazole-6,11-diones by double Buchwald–Hartwig coupling reaction.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
-
References and Notes
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- 14 2-Bromo-3-(2-bromophenyl)naphthalene-1,4-dione (3) To a mixture of 2,3-dibromonaphthalene-1,4-dione (0.786 g, 2.49 mmol) and boronic acid (0.5 g, 2.49 mol%) in toluene (10 mL) was added Pd(PPh3)4 (0.172 g, 0.15 mmol) and 2 M aq Na2CO3 solution (5 mL). The resulting mixture was stirred at 80 °C overnight. After cooling the mixture was diluted with CH2Cl2, washed 3 times with H2O, and dried over MgSO4. After filtration and evaporation, the crude product was purified by silica gel chromatography (CH2Cl2–PE, 5:5) giving 3 as yellow crystals, mp 126 °C, yield 1.2 g (62%). 1H NMR (200 MHz, CDCl3): δ = 7.22 (dd, 1 H, J = 7.4, 1.8 Hz, ArH), 7.30–7.49 (m, 2 H, ArH), 7.7 (dd, 1 H, J = 7.9, 1.2 Hz, ArH), 7.76–7.85 (m, 2 H, Ar), 8.14–8.27 (m, 2 H, ArH). 13C NMR (50 MHz, CDCl3): δ = 122.0 (C), 127.6 (2 × CH), 127.8 (CH), 128.3 (C), 129.9 (CH), 130.8 (CH), 131.3 (C), 131.7 (C), 132.9 (CH), 134.3 (CH), 134.7 (CH), 136.2 (C), 140.4 (C), 150.2 (C), 178.0 (CO), 180.6 (CO). Anal. Calcd for C16H8Br2O2: C, 49.02; H, 2.06. Found: C, 49.65; H, 1.98.
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- 16 General Procedure for the Double Buchwald–Hartwig Reaction for the Synthesis of 5-Substituted 5H-benzo[b]carbazole-6,11-diones 6a–k A mixture of 2-bromo-3-(2-bromophenyl)naphthalene-1,4-dione (3, 0.1 g, 0.25 mmol), aniline (1.5 g, 0.38 mmol equiv) in toluene (10 mL), K2CO3 (105 g, 0.76 mmol), Pd(OAc)2 (0.0098 g, 0.05 mmol), and BINAP (0.042 g, 0.06 mmol) was placed in a 4 mL sealed vial in a Biotage microwave-reactor cavity. The mixture was irradiated at 100 °C for 2 h. After cooling, the reaction mixture was diluted with CH2Cl2, washed with H2O (3 × 40 mL), and dried over MgSO4. After filtration and evaporation, the crude product was purified by silica gel chromatography (CH2Cl2–PE, 5:5). 5-(4-Nitrophenyl)-5H-benzo[b]carbazole-6,11-dione (6a) Yellow solid; mp 287 °C. 1H NMR (200 MHz, CDCl3): δ = 7.15–7.20 (m, 1 H, ArH), 7.44–7.50 (m, 2 H, ArH), 7.65–7.79 (m, 5 H, ArH), 8.05 (dd, 2 H, J = 7.0, 1.7 Hz, ArH), 8.25 (dd, 2 H, J = 7.0, 1.0 Hz, ArH), 8.46–8.56 (m, 2 H, ArH). 13C NMR (50 MHz, CDCl3): δ = 111.5 (CH), 124.1 (C), 124.2 (CH), 124.9 (2 × CH), 125.3 (CH), 126.7 (2 × CH), 128.4 (CH), 129.0 (2 × CH), 133.3 (2 × C), 133.5 (CH), 133.9 (C), 134.3 (CH), 135.3 (C), 140.5 (C), 142.5 (C), 147.9 (C), 177.7 (CO), 181.7 (CO). Anal. Calcd for C22H12N2O4: C, 71.74; H, 3.28; N, 7.61. Found: C, 71.66; H, 3.22; N, 7.61.
- 17 Compounds 5a,b were formed by the same protocol but using Cs2CO3 as base. 2-(2-Bromophenyl)-3-(4-nitrophenylamino)naphthlene-1,4-dione (5a) Orange solid; mp 220 °C. 1H NMR (200 MHz, CDCl3): δ = 6.84 (d, 2 H, J = 8.9 Hz, ArH), 6.89–7.14 (m, 3 H, ArH), 7.31 (dd, 1 H, J = 8.0, 0.7 Hz, ArH), 7.70–7.87 (m, 4 H, ArH), 7.89 (s, 1 H, NH), 8.20 (dd, 2 H, J = 7.6, 1.4 Hz, ArH). 13C NMR (50 MHz, CDCl3) :δ = 119.4 (C), 122.8 (2 × CH), 123.5 (2 × CH), 124.6 (CH), 126.7 (CH), 127.2 (CH), 127.3 (CH), 129.9 (CH), 130.2 (C), 132.3 (CH), 133.0 (CH), 133.1 (C), 133.2 (C), 134.0 (C), 134.4 (CH), 140.8 (C), 143.1 (C), 143.7 (C), 181.6 (CO), 182.4 (CO). Anal. Calcd for C22H13BrN2O4: C, 58.82; H, 2.92; N, 6.24. Found: C, 85.77; H, 2.87; N, 6.33. 2-(2-Bromophenyl)-3-(phenylamino)naphthalene-1,4-dione (5b) Red solid; mp 161 °C.1H NMR (200 MHz, CDCl3): δ = 6.78–6.99 (m, 7 H, ArH), 7.24 (d, 1 H, J = 9.6 Hz, ArH), 7.69–7.82 (m, 3 H, ArH), 8.18 (dd, 2 H, J = 7.6, 1.4 Hz, ArH). 13H NMR (50 MHz, CDCl3): δ = 116.3 (C), 124.5 (2 × CH), 125.2 (CH), 125.3 (C), 126.5 (CH), 126.6 (CH), 127.0 (CH), 127.9 (2 × CH), 129.0 (CH), 130.4 (C), 132.3 (CH), 132.5 (CH), 132.8 (CH), 133.5 (C), 134.5 (C), 135.1 (CH), 136.9 (C), 141.9 (C), 181.6 (CO), 188.9 (CO).