Patent Application
20080027226
a) 4-Bromoaniline (58.14 mmol) is dissolved in 200 ml water using 174 mmol HCl. The mixture is cooled to 0° C. and sodium nitrite (58.1 mmol) in 30 ml water is added dropwise over 30 minutes. After 45 minutes the diazonium salt is added via cannula to a mixture of 1-amino-4-bromonaphthalene (58.14 mmol) in 300 ml ethanol at 0° C. After 2 hours sodium carbonate (80.2 mmol) in 100 ml water is added dropwise, producing a pH of 7. After an additional 30 minutes the red precipitate is filtered and washed with water (2×300 ml). The brown-red solid was triturated in 100 ml methanol overnight, filtered and dried. The product was dried in vacuo to give a bright red solid (yield: 91%). 1H NMR (ppm, (CD3)2SO): 8.59 (d, 1H), 8.12 (s, 1H), 8.07 (d, 1H), 8.04 (d, 2H), 7.82 (d, 1H), 7.76 (d, 2H), 7.70 (t, 1H).
b) The product from step a) (49.37 mmol) and copper(II) acetate (0.49 mmol) are placed in a 250 ml flask with a stir bar. 250 ml tert-amyl alcohol are added and the mixture is heated to 80° C. tert-Butyl hydroperoxide, (98.7 mmol) is slowly added and the reaction is monitored by TLC. The flask is cooled to room temperature and the product is filtered. Washing with tert-amyl alcohol and removal of volatiles in vacuo give a light brown solid. The product is triturated in 30 ml methanol overnight, filtered and dried to give an off-white solid (yield: 77%). 1H NMR (ppm,, CDCl3): 8.47 (m, 1H), 8.20 (d, 1H), 8.08 (d, 2H), 8.01 (s, 1H), 7.58 (m, 2H), 7.49 (d, 2H).
c) Magnesium turnings (68.7 mmol) are dry stirred under argon for one hour. 32 ml ether are added, followed by 2 drops of dibromoethane. 4-Bromo-4′-tert-butylbiphenyl (Murphy, S., et. al. J. Org. Chem. 1995, 60, 2411) (34.6 mmol) in 20 ml ether and 25 ml THF is added dropwise over 1 hour. The mixture is refluxed for 2 hours at 37° C. In a separate flask triisopropylborate (41 mmol) and 30 ml THF are cooled to −78° C. under argon. The above Grignard reagent is added via cannula and the reaction is allowed to stir at −78° C. for 1 hour. The flask is warmed to room temperature and stirred for an additional hour. The mixture is poured into a flask containing HCl/water and is stirred for 2 hours. The beige product is filtered and washed with water. Removal of volatiles in vacuo give an off-white solid (yield: 64%). Tm=192° C. 1H NMR (ppm, (CD3)2SO): 7.80 (d, 2H), 7.55 (two overlapping doublets, 4H), 7.41 (d, 2H), 1.25 (s, 9H).
d) The product from step b) (0.94 mmol), the product from step c) (2.83 mmol), palladium tetrakis(triphenylphosphine) (8.6 μmol) and 10 ml N,N-dimethylacetamide are placed in a 100 ml flask and purged with argon for 2 hours. Tetraethylammonium hydroxide (20% in water) is placed in a 50 ml flask and purged with argon for 2 hours. Then 2.0 ml of the base solution (2.8 mmol) are added to the first flask under argon. The mixture is heated to 100° C. overnight and cooled. TLC showed one spot (hexanes:ethyl acetate, 1:1). 20 ml water are added and the product is removed via filtration. Washing with 20 ml water, followed by 20 ml methanol and drying in vacuo give a tan solid (yield: 87%). The product was subsequently purified using zone sublimation. MS (EI): 662 (M+1).
The product from example 1b) (2.48 mmol), 9,9-dimethylfluorene-2-boronic acid (EP-A-1238981, 7.44 mmol), palladium tetrakis(triphenylphosphine) (22 μmol), and 25 ml N,N-dimethylacetamide are placed in a 100 ml flask and purged with argon for 2 hours. Tetraethylammonium hydroxide (20% in water) is placed in a 50 ml flask and purged with argon for 2 hours. Then 5.3 ml of the base solution (7.5 mmol) are added to the first flask under argon. The mixture is heated to 100° C. overnight and cooled. 50 ml water are added and the product is removed via filtration. Washing with 100 ml water, followed by 30 ml methanol and drying in vacuo give a tan solid (yield: 90%). The product is subsequently purified using zone sublimation. MS (EI): 630 (M+1).
5-Amino-2-phenyl-2H-benzotriazole (Kehrmann, et. al., Chem. Ber. 1892, 25, 899.) (23.8 mmol), and potassium carbonate (52.3 mmole) are placed in a 250 ml flask with 50 ml DMF and a stir bar. While stirring, 1,5-dibromopentane (26.2 mmol) is added via syringe. The mixture is heated to 100° C. for 25 hours. The flask is cooled and the product is extracted using water:dichloromethane. Washing with water and extraction followed by removal of volatiles in vacuo give a dark yellow-green solid. The material is chromatographed using 19:1 hexanes:ethyl acetate (yield: 55%). Tm=143° C. 1H NMR (ppm, CDCl3): 8.30 (d, 2H), 7.78 (d, 1H), 7.54 (m, 2H), 7.45 (t, 1H), 7.30 (d, 2H), 7.13 (s, 1H), 3.26 (m, 4H), 1.80 (m, 4H), 1.67 (m, 2H). The material has a λmax emission of 458 nm in toluene, which corresponds to a color point of CIE (0.139, 0.116).
a) Bromophenylhydrazine hydrochloride (0.231 mol), 1-chloro-2,4-dinitrobenzene (0.115 mol) and sodium acetate trihydrate (0.346 mol) are placed in a 1 l reactor. 200 ml Ethanol are added and the mixture is heated to reflux for 6 hours. The mixture is cooled to room temperature and the product is removed by filtration. The material is washed with methanol, water and then methanol again. Volatiles are removed in vacuo to give a light brown solid (yield: 54%). Tm=201° C. 1H NMR (ppm, CDCl3): 8.94 (d, 1H), 8.30 (overlapping d and dd, 3H), 8.07 (d, 1H), 7.74 (d, 2H).
b) The product from example 4a (46.69 mmol) and 200 ml ethanol are placed in a 350 ml reactor. Raney nickel, 8 mL of a 70% slurry, is added. Hydrazine hydrate (0.226 mol) is added in portions over 12 hours with vigorous stirring. After an additional 5 hours at room temperature, the product is filtered and washed with methanol. The material is slurried in 200 ml water and 120 ml concentrated hydrochloric acid (1.44 mol) are added slowly. After stirring for 20 hours, the product is filtered and washed with water. Washing with methanol and removal of volatiles in vacuo give a tan solid (yield: 67%). 1H NMR (ppm, OS(CD3)2): 8.19 (d, 2H), 7.97 (d, 1H), 7.83 (d, 2H), 7.45 (d, 1H), 7.28 (dd, 1H).
c) The product from example 4b (15.4 mmol) and potassium carbonate (46.5 mmol) are placed in a 250 ml flask with 60 ml DMF. While stirring, 1,5-dibromopentane (19.8 mmol) is added via syringe. The mixture is heated to 100° C. for 2 hours. Additional 1,5-dibromopentane (7.4 mmol) is added via syringe. Heating is continued for 20 hours. The product is extracted using dichloromethane-water and washed with water. The product is dried over silica and chromatographed using 19:1 hexanes:ethyl acetate. The material is isolated as a yellow solid (yield: 46%). 1H NMR (ppm, CDCl3): 8.18 (d, 2H), 7.75 (d, 1H), 7.65 (d, 2H), 7.30 (d, 1H), 7.08 (s, 1H), 3.25 (m, 4H), 1.79 (m, 4H), 1.65 (m, 2H).
d) The product from step 4c) (4.20 mmol), 4-biphenylboronic acid (2.83 mmol), palladium tetrakis(triphenylphosphine) (35 mmol) and 25 ml N,N-dimethylacetamide are placed in a 100 ml flask and purged with argon for 2 hours. Tetraethylammonium hydroxide, 20% in water, is placed in a 50 mL flask and purged with argon for 2 hours. Then, 4.6 mL of the base solution (6.5 mmol) are added to the first flask under argon. The mixture is heated to 100° C. overnight and cooled. TLC showed two spots (hexanes:ethyl acetate, 1:1). 20 ml Water are added and the product is removed via filtration. Washing with water (20 ml), followed by methanol (20 ml), and drying in vacuo give a yellow solid (yield: 85%). Tm=213° C. The product is subsequently purified using zone sublimation. MS (EI): 431 (M+1).
a) 2-Bromo-4,4′-di-tert-butyl-biphenyl (34.8 mmol) is dissolved in THF and the solution is cooled to −75° C. n-Butyl lithium (1.6 mol/l solution, 41.7 mmol) is added to the solution over 10 minutes. The mixture is stirred for 1 hour at −75° C. To the reaction mixture 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane (69.5 mmol) in THF is added dropwise over 15 minutes at −75° C. The flask is warmed to room temperature and stirred for 2 hours. The mixture is poured into H2O and extracted with ethylacetate. The organic layer is dried over MgSO4 and concentrated by evaporation. Column chromatography of crude product with hexane and hexane/ethylacetate (10/1) as eluent gives a white solid (yield: 74.1%). 1H NMR (ppm, CDCl3): 7.50 (d, 1H), 7.47 (dd, 1H), 7.34 (d, 2H), 7.27 (d, 1H), 7.17 (d, 2H), 3.28 (s, 12H), 1.23, (s, 9H), 1.06 (s, 9H).
b) The product from example 5b (5.1 mmol), 2-(4,4′-di-tert-butyl biphenyl-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane (12.7 mmol), palladium tetrakis(triphenylphosphine) (0.25 mmol), tetraethylammonium hydroxide (20% in water, 15.3 mmol) and 60 ml of N,N-dimethylacetamide are placed in a 200 ml flask. The mixture is stirred at 110° C. overnight and cooled. The mixture is then poured into H2O and extracted with ethylacetate. The organic layer is dried over MgSO4 and concentrated by evaporation. Column chromatography of the crude product with hexane as eluent gives a greenish black solid (yield: 63.5%). The product is subsequently purified using zone sublimation. 1H NMR (ppm, CDCl3): 8.60 (d, 1H), 8.20 (d, 2H), 7.31-7.62 (m, 12H), 7.25 (d, 2H), 7.09 (d, 2H), 7.03 (d, 2H), 6.99 (d, 2H), 1.40 (d, 18H), 1.26 (s, 9H), 1.11 (s, 9H).
a) 4-Bromophenylhydrazine HCl (0.39 mol), and NaOAc.3 H2O (0.59 mol) are placed in a 1.5 l flask with EtOH 550 ml. While stirring, 1-fluoro-4-bromo-2-nitrobenzene (0.20 mol) is added (by pouring). The slurry becomes slightly orange. The mixture is heated to reflux overnight (20 hours). After cooling to room temperature, the mixture is filtered and washed with EtOH. Without vacuum on the frit, water is added with stirring to dissolve the NaCl and NaF. Vacuum is applied and the process is repeated. Stirring twice with MeOH in the same manner and applying vacuum give a light yellow, crystalline solid. Volatiles are removed in vacuum. (Yield: 93.4%)
b) The product from example 6a (0.11 mol), and sodium hydrogen sulfite (0.11 mol) are placed in a 250 ml 3 neck round balloon with 200 ml DMF. While stirring, the reaction mixture is heated to 110° C. overnight. After cooling to room temperature, the mixture is poured into 300 ml ice water, and then the precipitate is filtered off and washed with 1000 ml water and 500 ml EtOH. Volatiles are removed in vacuum give a slightly beige powder. (Yield: 93.4%) 1H NMR (ppm, CDCl3): 8.21 (dd, 2H), 8.09 (d, 1H), 7.79 (dd, 1H), 7.67 (dd, 2H), 7.49 (dd, 1H).
c) The product from example 6b (4.24 mmol), carbazole (8.92 mmol), Cul (9.34 mmol), potassium carbonate (9.34 mmol) and 30 ml of N,N-dimethylacetamide are placed in a 100 ml flask. The mixture is stirred at 170° C. overnight and cooled. Cul is removed by filtration, the mixture is then poured into H2O and the generated solid is obtained by filtration. The solid is washed with H2O, EtOH and dried under reduced pressure. Column chromatography of the crude product with hexane as eluent gives a yellow solid (yield: 24.7%). 1H NMR (ppm, CDCl3): 8.66 (dd, 2H), 8.19 (m, 6H), 7.83 (dd, 2H), 7.67 (dd, 1H), 7.52 (dd, 4H), 7.46 (td, 4H), 7.34 (td, 4H).
The following device structure is prepared: ITO/CuPC/NPD/Compound A-1/TPBI/LiF/Al where ITO is indium tin oxide, CuPC is copper phthalocyanine, NPD is 4,4′-bis-(1naphthylphenylamino) biphenyl, and TPBI is 1,3,5-tris-(N-phenyl-benzimidazol-2-yl) benzene. Using this device structure, a maximum brightness of 2200 cd/m2 is observed at a maximum efficiency of 0.67 cd/A with an emission λmax at 450 nm.
The following device structure is prepared: ITO/CuPC/NPD/Compound A-8/TPBI/LiF/Al. Using this device structure, a maximum brightness of 3400 cd/m2 is observed at a maximum efficiency of 0.83 cd/A with an emission λmax at 467 nm.
The following device structure is prepared: ITO/CuPC/NPD/Compound A-1+Compound B-2 (2.3% by weight)/TPBI/LiF/Al. Using this device structure, a maximum brightness of 6800 cd/m2 is observed at a maximum efficiency of 1.6 cd/A with an emission at CIE (0.148, 0.122).
The following device structure is prepared: ITO/CuPC/NPD/Compound A-1+Compound B-1 (1.6% by weight)/TPBI/LiF/Al. Using this device structure, a maximum brightness of 7600 cd/m2 is observed at a maximum efficiency of 1.6 cd/A with an emission at CIE (0.161, 0.131).
The following device structure is prepared: ITO/CuPC/TCTA/Compound A-13/TPBI/LiF/IA where ITO is indium tin oxide, CuPC is copper phthalocyanine, TCTA is 4,4′,4″-tri-(N-carbazoyl)triphenylamine, and TPBI is 1,3,5-tris-(N-phenyl-benzimidazol-2-yl) benzene. Using this device structure, a brightness of 146 cd/m2 is observed with a efficiency of 0.37 cd/A at 12 V with an emission λmax at 440 nm.
The following device structure is prepared: ITO/CuPC/TCTA/Compound A-13+Compound B-9 (1.6% by weight)/TPBI/LiF/Al. Using this device structure, a brightness of 114 cd/m2 is observed with a efficiency of 0.53 cd/A at 12 V with an emission λmax at 440 nm.
The following device structure is prepared: ITO/CuPC/TCTA/Compound A-13+Compound D-8 (1.7% by weight)/TPBI/LiF/Al. Using this device structure, a brightness of 161 cd/m2 is observed with a efficiency of 0.57 cd/A at 12 V with an emission λmax at 437 nm.
| Number | Date | Country | Kind |
|---|---|---|---|
| 03104562.8 | Dec 2003 | EP | regional |
| 04104279.7 | Sep 2004 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP04/53111 | 11/26/2004 | WO | 00 | 3/22/2007 |
