1-FUNCTIONALIZED DIBENZOFURANS AND DIBENZOTHIOPHENES FOR ORGANIC LIGHT EMITTING DIODES (OLEDS)

Abstract

The present invention relates to compounds of formula(I), a process for their production and their use in electronic devices, especially electroluminescent devices. When used as charge transport material and/or host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency and reduced driving voltage of electroluminescent devices.

##STR00001##

Claims

1. A compound of the formula ##STR00247## wherein X is O or S; Y is a group of formula —[Ar.sup.1].sub.a—[Ar.sup.2].sub.b—[Ar.sup.3].sub.c—A.sup.1; A.sup.1 is a group of formula ##STR00248## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 and R.sup.23 are independently of each other H, F, CN, NO.sub.2, Si(R.sup.24)(R.sup.25)(R.sup.26), P(O)(R.sup.27)(R.sup.28), N(R.sup.30)(R.sup.31), a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E, and or interrupted by D, a C.sub.3-C.sub.18cycloalkyl group, which can optionally be substituted by G, or a group of formula —[Ar.sup.4].sub.d—[Ar.sup.5].sub.e—[Ar.sup.6].sub.f—A.sup.2, a is 0, or 1, b is 0, or 1, c is 0, or 1, d is 0, or 1, e is 0, or 1, f is 0, or 1, Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, Ar.sup.5 and Ar.sup.6 are independently of each other a C.sub.6-C.sub.24arylene group, which can optionally be substituted by G, a C.sub.2-C.sub.30heteroarylene group, which can optionally be substituted by G, A.sup.2 is H, F, CN, NO.sub.2, Si(R.sup.24)(R.sup.25)(R.sup.26), P(O)(R.sup.27)(R.sup.28), N(R.sup.30)(R.sup.31), a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E, and or interrupted by D, a C.sub.3-C.sub.18cycloalkyl group, which can optionally be substituted by G, a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; R.sup.24, R.sup.25, R.sup.26, R.sup.27, and R.sup.28 are independently of each other a C.sub.1-C.sub.25alkyl group, a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; R.sup.30 and R.sup.31 are independently of each other a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.65—, —SiR.sup.70R.sup.71—, —POR.sup.72—, —CR.sup.63═CR.sup.64—, or —C≡C—, E is —OR.sup.69, —SR.sup.69, —NR.sup.65R.sup.66, —COR.sup.68, —COOR.sup.67, —CONR.sup.65R.sup.66, —CN, F, or NO.sub.2; G is E, or a C.sub.1-C.sub.18alkyl group, a C.sub.3-C.sub.18cycloalkyl group, a C.sub.6-C.sub.24aryl group, a C.sub.6-C.sub.24aryl group, which is substituted by F, —CN, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by O; a C.sub.2-C.sub.50heteroaryl group, or a C.sub.2-C.sub.50heteroaryl group, which is substituted by F, —CN, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is interrupted by O; R.sup.63 and R.sup.64 are independently of each other H, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.65 and R.sup.66 are independently of each other a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; or R.sup.65 and R.sup.66 together form a five or six membered ring; R.sup.67 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.68 is H; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.69 is a C.sub.6-C.sub.18aryl; a C.sub.6-C.sub.18aryl, which is substituted by C,-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.70 and R.sup.71 are independently of each other a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, and R.sup.72 is a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; with the proviso that in case A.sup.1 is a group of formula (Xa), at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is a group of formula —[Ar.sup.4].sub.d—[Ar.sup.5].sub.e—[Ar.sup.6].sub.f—A.sup.2, wherein A.sup.2 is a group of formula (Xb).

2. The compound according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are independently of each other H, or a group of formula —[Ar.sup.4].sub.d—[Ar.sup.5].sub.e—[Ar.sup.6].sub.f—A.sup.2, wherein d, e, f, Ar.sup.4, Ar.sup.5, Ar.sup.6 and A.sup.2 are defined in claim 1.

3. The compound according to claim 1, which is a compound of formula ##STR00249## wherein R.sup.3, R.sup.4 and R.sup.6 are independently of each other H, or a group of formula —[Ar.sup.4].sub.d—[Ar.sup.5].sub.e—[Ar.sup.6].sub.f—A.sup.2, and Y, X, d, e, f, Ar.sup.4, Ar.sup.5, Ar.sup.6 and A.sup.2 are defined in claim 1.

4. The compound according to claim 3, which is a compound of formula ##STR00250## wherein R.sup.4 and R.sup.6 are independently of each other H, or a group of formula —[Ar.sup.4].sub.d—[Ar.sup.5].sub.e—[Ar.sup.6].sub.f—A.sup.2, and Y, X, d, e, f, Ar.sup.4, Ar.sup.5, Ar.sup.6 and A.sup.2 are defined in claim 3.

5. The compound according to claim 1, wherein Y is a group of formula —[Ar.sup.1].sub.a—[Ar.sup.2].sub.b—[Ar.sup.3].sub.c—A.sup.1, wherein a is 0, b is 0, c is 0, and A.sup.1 is a group of formula ##STR00251## wherein R.sup.10, R.sup.13, R.sup.18and R.sup.21 are independently of each other H, a group of formula ##STR00252## wherein X.sup.1, X.sup.2 and X.sup.3 are independently of each other N, or CH, with the proviso that at least one of X.sup.1, X.sup.2 and X.sup.3 represent N, and R.sup.73 and R.sup.74 are independently of each other H, or a phenyl group.

6. The compound according to claim 1, wherein in the group of formula —[Ar.sup.4].sub.d—[Ar.sup.5].sub.e—[Ar.sup.6].sub.f—A.sup.2, wherein d is 0, or 1, e is 0, or 1, f is 0, or 1, Ar.sup.4, Ar.sup.5 and Ar.sup.6 are independently of each other ##STR00253## wherein X.sup.4′, X.sup.5′, X.sup.6′, X.sup.7 and X.sup.8 are independently of each other N, or CH, with the proviso that at least one of X.sup.4′, X.sup.5′ and X.sup.6′ represents N; R.sup.77 and R.sup.78 are independently of each other H, or a phenyl group, and R.sup.79 is a phenyl group, or a group of formula ##STR00254## A.sup.2 is H, a group of formula (Xa), (Xb), ##STR00255## wherein X.sup.4, X.sup.5 and X.sup.6 are independently of each other N, or CH, with the proviso that at least one of X.sup.4, X.sup.5 and X.sup.6 represent N; R.sup.37, R.sup.38, R.sup.39, R.sup.40 and R.sup.41 are independently of each other H, or a phenyl group, and R.sup.75 and R.sup.76 are independently of each other H, or a phenyl group.

7. The compound according to claim 6, wherein d is 0, or 1, e is 0, or 1, f is 0, or 1, Ar.sup.4, Ar.sup.5 and Ar.sup.6 are independently of each other ##STR00256## wherein X.sup.4′, X.sup.5′, X.sup.6′, X.sup.7 and X.sup.8 are independently of each other N, or CH, with the proviso that at least one of X.sup.4′, X.sup.5′ and X.sup.6′ represents N; R.sup.77 and R.sup.78 are independently of each other H, or a phenyl group, and R.sup.79 is a phenyl group, or a group of formula ##STR00257## A.sup.2 is H, a group of formula ##STR00258## ##STR00259## wherein X.sup.4, X.sup.5 and X.sup.6 are independently of each other N, or CH, with the proviso that at least one of X.sup.4, X.sup.5 and X.sup.6 represent N; R.sup.37, R.sup.38, R.sup.39, R.sup.40 and R.sup.41 are independently of each other H, or a phenyl group, R.sup.75 and R.sup.76 are independently of each other H, or a phenyl group, R.sup.10, R.sup.13, R.sup.18 and R.sup.21 are independently of each other H, a group of formula ##STR00260## wherein X.sup.1, X.sup.2 and X.sup.3 are independently of each other N, or CH, with the proviso that at least one of X.sup.1, X.sup.2 and X.sup.3 represent N, and R.sup.73 and R.sup.74 are independently of each other H, or a phenyl group.

8. The compound according to claim 1, wherein the group of formula —[Ar.sup.4].sub.d—[Ar.sup.5].sub.e—[Ar.sup.6].sub.f—A.sup.2 is H, or a group of formula ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267##

9. The compound according to claim 1, wherein X is O.

10. The compound according to claim 1, which is a compound of formula ##STR00268## wherein R.sup.4 and R.sup.6 are H, a group of formula ##STR00269## ##STR00270## ##STR00271## ##STR00272## Y is a group of formula ##STR00273## wherein R.sup.10 is H, or a group of formula ##STR00274## R.sup.18 is H, or a group of formula ##STR00275## and R.sup.13 and R.sup.21 are H, with the proviso that in case Y is a group of formula (Xb-1), R.sup.4 and R.sup.6 are a group of formula (XIa), (XIe), (XIg), (XIj), (XIs), (XIw), (XIIb), (XIIc), or (XIII).

11. An electronic device, comprising the compound according claim 1.

12. The electronic device according to claim 11, which is an electroluminescent device.

13. A charge transport layer, a charge/exciton blocker layer, or an emitting layer comprising the compound according to claim 1.

14. The emitting layer according to claim 13, comprising the compound as host material in combination with a phosphorescent emitter.

15. An apparatus selected from the group consisting of stationary visual display units; mobile visual display units; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising the organic electronic device according to claim 11.

16. An electrophotographic photoreceptor, a photoelectric converter, an organic solar cell, a switching element, an organic light emitting field effect transistor, an image sensor, a dye laser, or an electroluminescent device comprising the compound according to claim 1.

17. A compound of formula ##STR00276## wherein X is O or S; R.sup.4 and R.sup.6 are independently of each other F, CN, NO.sub.2, Si(R.sup.24)(R.sup.25)(R.sup.26), P(O)(R.sup.27)(R.sup.28), N(R.sup.30)(R.sup.31), a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E, and or interrupted by D, a C.sub.3-C.sub.18cycloalkyl group, which can optionally be substituted by G, or a group of formula —[Ar.sup.4].sub.d—[Ar.sup.5].sub.e—[Ar.sup.6].sub.f—A.sup.2, d is 0, or 1, e is 0, or 1, f is 0, or 1, Ar.sup.4, Ar.sup.5 and Ar.sup.6 are independently of each other a C.sub.6-C.sub.24arylene group, which can optionally be substituted by G, a C.sub.2-C.sub.30heteroarylene group, which can optionally be substituted by G, A.sup.2 is H, F, CN, NO.sub.2, Si(R.sup.24)(R.sup.25)(R.sup.26), P(O)(R.sup.27)(R.sup.28), N(R.sup.30)(R.sup.31), a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E, and or interrupted by D, a C.sub.3-C.sub.18cycloalkyl group, which can optionally be substituted by G, a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; R.sup.24, R.sup.25, R.sup.26, R.sup.27, and R.sup.28 are independently of each other a C.sub.1-C.sub.25alkyl group, a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; R.sup.30 and R.sup.31 are independently of each other a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —SiR.sup.70R.sup.71—, —POR.sup.72—, —CR.sup.63═CR.sup.64—, or —C≡C—, E is —OR.sup.69, —SR.sup.69, —NR.sup.65R.sup.66, —COR.sup.68, —COOR.sup.67, —CONR.sup.65R.sup.66, —CN, F or NO.sub.2; G is E, or a C.sub.1-C.sub.18alkyl group, a C.sub.3-C.sub.18cycloalkyl group, a C.sub.6-C.sub.24aryl group, a C.sub.6-C.sub.24aryl group, which is substituted by F, —CN, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by O; a C.sub.2-C.sub.50heteroaryl group, or a C.sub.2-C.sub.50heteroaryl group, which is substituted by F, —CN, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is interrupted by O; R.sup.63 and R.sup.64 are independently of each other H, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.65 and R.sup.66 are independently of each other a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; or R.sup.65 and R.sup.66 together form a five or six membered ring; R.sup.67 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.68 is H; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.69 is a C.sub.6-C.sub.18aryl; a C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.70 and R.sup.71 are independently of each other a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, and R.sup.72 is a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl.

18. A process for preparing the compound of claim 1 having the formula ##STR00277## comprising a) reacting a compound of formula ##STR00278## with a compound of formula ##STR00279## in the presence of a base in a solvent at room temperature to reflux temperature of the solvent, wherein Y, X, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 and R.sup.23 are defined in claim 1.

19. An apparatus selected from the group consisting of stationary visual display units; mobile visual display units; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising the charge transport layer, the charge/exciton blocker layer, or the emitting layer according to claim 13.

Description

EXAMPLES

Example 1

[0343] ##STR00214##

[0344] a) 1-Bromo-2,3-difluorobenzene (3.00 g, 15.45 mmol) and 2-fluoro-6-methoxybenzeneboronic acid (3.96 g, 23.32 mmol) were dissolved in THF (78 mL). To this solution potassium fluoride (2.71 g, 46.64 mmol) dissolved in water (8 mL) was added. To this solution tris(dibenzylideneacetone)dipalladium (0) (Pd.sub.2(dba).sub.3) (711 mg, 0.78 mmol) and 1 M tri-tert-butylphosphine (.sup.tBu.sub.3P) in toluene (1.55 mL) were added, and then the mixture was stirred at 60° C. for 18 h. After the reaction mixture was cooled to room temperature, a solid was removed by filtration. To the filtrate was water added, and the aqueous layer was extracted with tert-butyl methyl ether. The combined organic layer was washed with brine. After drying over MgSO.sub.4, the solvent was removed under reduced pressure to give yellowish oil. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and tert-butyl methyl ether (95:5) to yield 2.33 g (63%) of 1,2-difluoro-3-(2-fluoro-6-methoxy-phenyl)benzene (C-1) as a yellow oil.

[0345] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.40-7.33 (m, 2H), 7.25-7.10 (m, 3H), 6.85-6.80 (m, 2H), 3.82 (s, 3H)

##STR00215##

[0346] b) Compound C-1 (5.27 g, 22.1 mmol) was dissolved in CH.sub.2Cl.sub.2 (75 mL), and the solution was cooled at −78° C. To the solution was 1 M boron tribromide in heptane (26.5 mL, 26.5 mmol) added dropwise under N.sub.2 atomosphere, and then the mixture was stirred overnight. The reaction mixture was poured into ice-water, and the aqueous layer was extracted with CH.sub.2Cl.sub.2. The combined organic layer was washed with water. After drying over MgSO.sub.4, the solvent was removed under reduced pressure to give dark brown oil. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and ethyl acetate (6:1) to yield 5.10 g (97%) of 2-(2,3-difluorophenyl)-3-fluoro-phenol C-2 as brown resin. Compound C-2 was used for the next reaction without further purification.

##STR00216##

[0347] c) Compound C-2 (11.43 g, 51.0 mmol) was dissolved in N-methylpyrrolidone (NMP) (101 mL). To the solution potassium carbonate (14.09 g, 102.0 mmol) was added, and the mixture was stirred at 150° C. overnight. After the reaction mixture was cooled at room temperature, it was diluted with 300 mL of water to give a solid. It was collected by filtration, and it was purified by column chromatography on silica gel eluting with heptane to yield 6.96 g of 1,6-difluorodibenzofuran (C-3) as a white solid.

[0348] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.86 (dd, J=7.6, 1.3 Hz, 1H), 7.52-7.44 (m, 2H), 7.37-7.23 (m, 2H). 7.13-7.05 (m, 1H)

##STR00217##

[0349] c) Intermediate C-3 (2.23 g, 10.9 mmol), benzimidazolo[1,2-a]benzimidazole (2.26 g, 10.9 mmol), and potassium phosphate (2.78 g, 13.1 mmol) were suspended in NMP (66 mL). The mixture was stirred at 150° C. for 48 h. After the reaction mixture was cooled at room temperature, 66 mL of EtOH and 244 mL of water were added there to give a solid. This solid was collected by filtration, and it was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and CHCl.sub.3 to yield 1.74 g (41%) of compound 1-1 as a white solid. LC-MS (m/z) 391

##STR00218##

[0350] d) Compound 1-1 (1.7 g, 4.3 mmol), carbazole (762 mg, 4.5 mmol), and potassium phosphate (1.94 g, 9.1 mmol) were suspended in NMP (22 mL). The mixture was stirred at 190° C. overnight. After the reaction mixture was cooled at room temperature, 90 mL of water was added to the reaction mixture to give a solid. It was collected by filtration, and it was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and CHCl.sub.3 to yield B-50 (1.83 g (78%)) as a white solid.

[0351] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 8.26-8.22 (m, 2H), 8.03-7.96 (m, 2H), 7.82-7.79 (m, 1H), 7.72-7.63 (m, 4H), 7.52-7.33 (m, 8H), 7.30-7.23 (m, 4H), 7.08 (dd, J=7.9, 1.1 Hz, 1H) LC-MS (m/z) 538

Example 2

[0352] ##STR00219##

[0353] a) Intermediate C-3 (2.5 g, 12.0 mmol) and benzoimidazolo[1,2-a]benzimidazole (6.0 g, 29 mmol) were entered in N-methylpyrrolidone (35 mL). To the mixture was potassium phosphate (12.4 g, 58.1 mmol) added, and the mixture was stirred at 190° C. for 32 h. After the reaction mixture was cooled at room temperature, 50 mL of water was poured into the reaction mixture to give a brown solid. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of ethyl acetate and CH.sub.2Cl.sub.2 to yield compound B-49 (3.9 g (56%)) as a white solid. LC-MS (m/z) 579 (M+1).

[0354] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.98-7.96 (m, 2H), 7.91-7.90 (m, 2H), 7.83 (d, J=8.5 Hz, 1H), 7.78-7.68 (m, 4H), 7.48-7.24 (m, 11H), 7.14 (d, J=7.8 Hz, 1H), 7.04 (d, J=8.5 Hz, 1H)

Example 3

[0355] ##STR00220##

[0356] a) Intermediate C-3 (1.55 g, 4.4 mmol), carbazole (762 mg, 4.5 mmol), and potassium phosphate (1.94 g, 9.1 mmol) were suspended in NMP (22 mL). The mixture was stirred at 190° C. overnight. After the reaction mixture was cooled at room temperature, 90 mL of water was added to the reaction mixture to give a solid. It was collected by filtration, and it was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and CHCl.sub.3 to yield 1.83 g (78%) of 3-1 as a white solid.

[0357] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 8.29-8.23 (m, 2H), 7.83 (dd, J=1.0, 8.3 Hz, 1H), 7.77-7.71 (m, 1H), 7.57 (dd, J=1.0, 7.6 Hz, 1H), 7.41-7.32 (m, 4H), 7.18-7.10 (m, 3H), 6.89-6.82 (m, 1H), 6.23 (dd, J=1.0, 8.0 Hz, 1H)

##STR00221##

[0358] b) Compound 3-1 (1.55 g, 4.4 mmol), benzimidazolo[1,2-a]benzimidazole (960 mg, 4.6 mmol), and potassium phosphate (1.97 g, 9.3 mmol) were suspended in NMP (22 mL). The mixture was stirred at 190° C. for 18.5 h. After the reaction mixture was cooled at room temperature, 44 mL of EtOH and 22 mL of water were added to the reaction mixture to give a solid. It was collected by filtration, and it was purified by column chromatography on silica gel eluting with a mixed solvent of toluene and CHCl.sub.3.The product was further purified by recrystallization with toluene and cyclohexane to result in compound A-10 (yield: 1.55 g (65%)) as a white solid. LC-MS (m/z) 538.

[0359] .sup.1H-NMR (300 MHz, DMSO-d6): δ 8.42-8.39 (m, 2H), 8.32-8.25 (m, 2H), 7.95-7.82 (m, 3H), 7.72 (dd, J=1.2, 7.6 Hz, 1H), 7.61-7.58 (m, 1H), 7.50-7.32 (m, 9H), 7.25 (t, J=7.9 Hz, 1H), 7.20-7.17 (m, 2H), 6.38 (dd, J=1.1, 8.0 Hz, 1H)

Example 4

[0360] ##STR00222##

[0361] a) 5.3 g of 4-Bromo-2-iodoaniline and 3.63 g of 6-fluoro-2-methoxyphenyl boronic acid were dissolved in 346 mL of toluene and 201 mL of ethanol. Separately, 7.38 g of potassium carbonate was dissolved in 56 mL of water, and the solution was added there. After 616 mg of Pd(PPh.sub.3).sub.4 was added there, the mixture was stirred at 80° C. for 48 h. After the reaction mixture was cooled at room temperature, the reaction mixture was partly evaporated, and diluted with water and toluene. The aqueous layer was extracted with toluene. The organic layers were washed with brine, dried with Na.sub.2SO.sub.4. After Na.sub.2SO.sub.4 was removed by filtration and evaporated to give 6.38 g of dark-brown oil. The product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and ethyl acetate (3:1) to yield 4.25 g (81%) 4-bromo-2-(2-fluoro-6-methoxy-phenyl)aniline (D-1) as a light brown resin.

[0362] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.39-7.28 (m, 2H), 7.22 (d, J=7.2 Hz, 1H), 6.87-6.80 (m, 2H), 6.71 (d, J=6.7 Hz, 1H), 3.82 (s, 3H)

##STR00223##

[0363] b) Compound D-1 (12.3 g, 41.54 mmol) was dissolved in trifluoroacetic acid (69 mL), and the solution was cooled at 0° C. Sodium nitrite (3.44 g, 49.84 mmol) dissolved in water (6.9 mL) was added dropwise there. After completion of the addition, the mixture was stirred at 70° C. for 2 h. After the reaction mixture was cooled at room temperature, it was diluted with 70 mL of ethanol to give a solid. The solid was collected by filtration, and the crude product was purified by column chromatography on silica gel eluting with cyclohexane to yield 7.09 g (58%) of 2-bromo-8-fluorodibenzofuran (D-2) as a white solid.

[0364] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 8.21 (dd, J=0.5, 2.0 Hz, 1H), 7.61 (dd, J=2.0, 8.7 Hz, 1H), 7.50-7.37 (m, 3H), 7.11-7.05 (m, 1H)

##STR00224##

[0365] c) Intermediate D-2 (2.1 g, 7.9 mmol) and 9[-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole (4 g, 8.7 mmol) were dissolved in 103 mL of toluene and 53 mL of EtOH. To the solution was potassium carbonate (3.28 g, 23.8 mmol) dissolved in 18 mL of water added. After Pd(PPh.sub.3).sub.4 (274 mg, 0.24 mmol) was added there, the mixture was stirred at 80° C. for 48 h. After the reaction mixture was cooled at room temperature, it was diluted with water and toluene. Then, the aqueous layer was extracted with toluene. The organic layer was washed with brine, and dried with Na.sub.2SO.sub.4. After removal of Na.sub.2SO.sub.4 by filtration, the filtrate was concentrated to give a white solid. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of cyclohexane and toluene to yield 4.26 g (99%) of compound 4-1 as a white solid. LC-MS (m/z) 517.

[0366] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 8.35-8.34 (m, 1H), 8.25-8.19 (m, 4H), 7.89-7.76 (m, 4H), 7.70-7.67 (m, 2H), 7.47-7.42 (m, 6H), 7.37-7.31 (m, 2H), 7.12-7.06 (m, 1H)

##STR00225##

[0367] d) Compound 4-1 (3 g, 5.8 mmol), benzimidazolo[1,2-a]benzimidazole (1.26 g, 6.1 mmol), and potassium phosphate (2.58 g, 12.2 mmol) were suspended in NMP (29 mL). The mixture was stirred at 190° C. for 48 h. After the reaction mixture was cooled at room temperature, 58 mL of EtOH and 29 mL of water were added to the reaction mixture to give a solid. It was collected by filtration, and it was purified by column chromatography on silica gel eluting with a mixed solvent of toluene and CHCl.sub.3. Then, the product was recrystallized with toluene and heptane. The formed solid was collected by filtration and dried in vacuum to yield 2.39 g (59%) of compound (B-25) as a white solid. LC-MS (m/z) 704.

[0368] .sup.1H-NMR (300 MHz, DMSO-d6): δ 8.39-8.36 (m, 2H), 8.15-8.12 (m,1H), 8.01-7.72 (m, 9H), 7.61-7.25 (m, 13H), 7.01(d, J=1.4 Hz, 1H), 7.54 (td, J=7.5, 1.2 Hz, 1H), 6.57 (td, J=7.5, 1.2 Hz, 1H)

Example 5

[0369] ##STR00226##

[0370] a) Intermediate D-2 (2.12 g, 8.0 mmol), carbazole (1.34 g, 8.0 mmol) and sodium tert-butoxide (1.08 g 11.2 mmol) were added to toluene (40 mL). To the suspension were .sup.tBu.sub.3P-HBF.sub.4 (185 mg, 0.64 mmol) and Pd.sub.2(dba).sub.3 (146 mg, 0.16 mmol) added, and the mixture was refluxed for 48 h. After the reaction mixture was cooled at room temperature, it was diluted with 40 mL of cyclohexane. The solid was removed by filtration, and the filtrate was concentrated to give compound 5-1 as a colorless resin. LC-MS (m/z) 517.

[0371] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 8.27 (dd, J=0.5, 2.1 Hz, 1H), 8.22-8.19 (m, 2H), 7.81 (dd, J=0.5, 8.7 Hz, 1H), 7.68 (dd, J=2.1, 8.7 Hz, 1H), 7.55-7.39 (m, 6H), 7.36-7.31 (m, 2H), 7.14-7.08 (m, 1H)

##STR00227##

[0372] b) Compound 5-1 (321 mg, 0.9 mmol), benzimidazolo[1,2-a]benzimidazole (199 mg, 0.96 mmol), and potassium phosphate (407 g, 1.92 mmol) were added to NMP (5 mL). The mixture was stirred at 190° C. overnight. After reaction mixture was cooled at room temperature, it was diluted with 10 mL of EtOH and 5 mL of water to give a solid. The solid was collected by filtration. The crude product was purified by by column chromatography on silica gel eluting with a mixed solvent of toluene and CH.sub.2Cl.sub.2 to yield 489 mg (99%) of compound B-7 as a white solid. LC-MS (m/z) 539 [M+H].sup.+

Example 6

[0373] ##STR00228##

[0374] a) 2-bromo-1,3-difluoro-benzene (11.52 g, 59.7 mmol), (2-methoxyphenyl)boronic acid (11.52 g, 75.8 mmol), potassium fluoride (10.94 g, 188.3 mmol), THF (240 mL), and water (24 mL) were entered into a flask. To this solution Pd.sub.2(dba).sub.3 (2.76 g, 3.01 mmol) and 1 M .sup.tBu.sub.3P in toluene (6 mL) were added, and then the mixture was refluxed for 48 h. After cooling down to room temperature, the reaction mixture was poured into water. The aqueous layer was extracted with ethyl acetate (AcOEt) and the combined organic layer was washed with brine. After drying over MgSO.sub.4, the solvent was removed under reduced pressure to give yellowish liquid. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and AcOEt (10:1) to yield 12.24 g (81%) of 1,3-difluoro-2-(2-methoxyphenyl)benzene (E-1) as a beige solid.

[0375] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.49-7.43 (m, 1H), 7.36-7.26 (m, 2H), 7.09-6.95 (m, 4H), 3.83 (s, 3H)

##STR00229##

[0376] b) Compound E-1 (12.24 g, 55.6 mmol) was dissolved in CH.sub.2Cl.sub.2 (200 mL), and the solution was cooled at −78° C. To the solution was 1 M boron tribromide in heptane (89 mL, 89 mmol) added dropwise under N.sub.2 atomosphere, and then the mixture was stirred overnight. The reaction mixture was poured into ice-water, and the aqueous layer was extracted with CH.sub.2Cl.sub.2. The combined organic layer was washed with water. After drying over MgSO.sub.4, the solvent was removed under reduced pressure to give 2-(2,6-difluorophenyl)phenol E-2 as yellowish liquid (11.42 g, 99%).

[0377] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.43-7.33 (m, 2H), 7.29-7.26 (m, 1H), 7.08-7.00 (m, 4H), 4.93 (br, 1H)

##STR00230##

[0378] c) Compound E-2 (12.08 g, 65 mmol) was dissolved in N-methylpyrrolidone (80 mL). To the solution was potassium carbonate (18.02 g, 130 mmol) added. Then, the mixture was stirred at 180° C. for 5 h. After the reaction mixture was cooled at room temperature, it was poured into water to give a solid. The solid was collected by filtration, washed with water, and dried over into a vacuum oven to give 10.8 g (99%) of 1-fluorodibenzofuran (E-3) as a white solid.

[0379] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 8.10 (dq, J=7.7, 0.8 Hz, 1H), 7.60 (dq, J=8.3, 0.7 Hz, 1H), 7.51 (td, J=8.3, 1.5 Hz, 1H), 7.49-7.38 (m, 3H), 7.10-7.04 (m, 1H)

##STR00231##

[0380] d) Intermediate (E-3) (1.3 g, 7.0 mmol) and benzoimidazolo[1,2-a]benzimidazole (1.52 g, 7.3 mmol) were entered in N-methylpyrrolidone (20 mL). To the mixture was potassium phosphate (3.12 g, 14.7 mmol) added, and the mixture was stirred at 180° C. for 40 h. After the reaction mixture was cooled at room temperature, 50 mL of water was poured into the reaction mixture to give a grey solid. The solid was collected by filtration, and washed with water and ethanol. The crude product was purified by column chromatography on silica gel eluting with CH.sub.2Cl.sub.2 to yield 1.87 g (71%) of compound (B-1) as a white solid.

[0381] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.98-7.95 (m, 2H), 7.81-7.73 (m, 4H), 7.63 (dt, J=0.8, 8.3 Hz, 1H), 7.45-7.35 (m, 4H), 730-7.26 (m, 1H), 7.12 (dt, J=0.8, 8.0 Hz, 1H), 7.04 (td, J=0.9, 7.6 Hz, 1H), 6.91 (dq, J=0.6, 1.5, 7.9 Hz, 1H)

Example 7

[0382] ##STR00232##

[0383] a) Intermediate (D-2) (2.8 g, 10.6 mmol) and 9-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole (4.6 g, 15.6 mmol) were dissolved in 50 mL of toluene. To the solution was potassium carbonate (3.28 g, 23.8 mmol) dissolved in 16 mL of water added. After Pd(PPh.sub.3).sub.4 (610 mg, 5.3 mmol) was added there, the mixture was stirred at 85° C. for 2 h. After the reaction mixture was cooled at room temperature, it was diluted with water and toluene. Then, the aqueous layer was extracted with toluene. The organic layer was washed with brine, and dried with Na.sub.2SO.sub.4. After removal of Na.sub.2SO.sub.4 by filtration, the filtrate was concentrated to give a white solid. The crude product was purified by column chromatography on silica gel eluting with toluene to yield 5.4 g (97%) of compound 7-1 as a white solid.

##STR00233##

[0384] b) Compound 7-1 (3.0 g, 7.0 mmol), benzimidazolo[1,2-a]benzimidazole (1.8 g, 8.4 mmol), and potassium phosphate (3.6 g, 29.8 mmol) were added to NMP (35 mL). The mixture was stirred at 190° C. for 8 h. After reaction mixture was cooled at room temperature, it was diluted with 40 mL of water to give a solid. The solid was collected by filtration, and it was washed with 100 mL of water. The crude product was purified by by column chromatography on silica gel eluting with toluene to yield 2.5 g (58%) of compound B-17 as a white solid. LC-MS (m/z) 615 [M+H].sup.+

Example 8

[0385] ##STR00234##

[0386] a) 2-bromo-4-(3-bromo-4-methoxy-phenyl)-1-methoxy-benzene (30.7 g, 82.5 mmol) and 2-fluoro-6-methoxybenzeneboronic acid (31.3 g, 198 mmol) were dissolved in THF (300 mL) and water (30 mL). To this solution Pd.sub.2(dba).sub.3 (7.55 g, 8.25 mmol), .sup.tBu.sub.3P—HBF.sub.4 (4.79 g, 16.5 mmol), potassium fluoride (28.8 g, 195 mmol) were added, and then the mixture was stirred at 60° C. for 8 h. After the reaction mixture was cooled to room temperature, the solvent was removed by evaporation. The crude product was dissolved in 1.5 L of CH.sub.2Cl.sub.2, and it was purified by column chromatography on silica gel eluting with CH.sub.2Cl.sub.2. The obtained product was suspended in 90 mL of toluene, and the suspension was stirred at 90° C. for 1 h. After it was cooled at room temperature, the solid was collected by filtration, and washed with hexane to yield 33.6 g (93%) of compound 8-1 as a white solid.

[0387] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.61 (dd, J=2.4, 8.8 Hz, 2H), 7.48 (d, J=2.4 Hz, 2H), 7.31-7.25 (m, 2H), 7.06 (d, J=8.8 Hz, 2H), 6.98-6.94 (m, 4H), 3.83 (s, 6H)

##STR00235##

[0388] b) Compound 8-1 (18.8 g, 42.9 mmol) was dissolved in CH.sub.2Cl.sub.2 (600 mL), and the solution was cooled at −78° C. To the solution was 1 M boron tribromide in CH.sub.2Cl.sub.2 (129 mL, 129 mmol) added dropwise under N.sub.2 atomosphere, and then the mixture was stirred 4 h. The reaction mixture was cooled at −60° C., and 60 mL of MeOH was added there. After the reaction mixture was warmed at room temperature, 240 mL of water was added there. The aqueous layer was extracted with CH.sub.2Cl.sub.2. The combined organic layer was washed with water. After drying over MgSO.sub.4, the solvent was removed under reduced pressure to give compound 8-2 as yellowish liquid (17.3 g, 98%).

[0389] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 7.53 (dd, J=2.3, 8.6 Hz, 2H), 7.44 (d, J=2.3 Hz, 2H), 7.38-7.33 (m, 6H), 7.07-7.01 (m, 6H), 4.90 (s, 2H)

##STR00236##

[0390] c) Compound 8-2 (17.3 g, 42.16 mmol) was dissolved in N-methylpyrrolidone (410 mL). To the solution was potassium carbonate (23.3 g, 168 mmol) added. Then, the mixture was stirred at 190° C. for 2 h. After the reaction mixture was cooled at room temperature, 600 mL of water was added to the reaction mixture. The solid was collected by filtration, washed with MeOH and hexane, and dried over into a vacuum oven to give 15.7 g (99%) of compound 8-3 as a white solid.

[0391] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ 8.32 (d, J=1.9 Hz, 2H), 7.80 (dd, J=2.1, 8.1 Hz, 2H), 7.67 (d, J=8.6 Hz, 2H), 7.46-7.39 (m, 4H), 7.10-7.06 (m, 2H)

##STR00237##

[0392] d) Compound 8-3 (3.0 g, 8.10 mmol), benzimidazolo[1,2-a]benzimidazole (1.85 g, 8.91 mmol), and potassium phosphate (1.96 g, 16.2 mmol) were added to NMP (30 mL). The mixture was stirred at 190° C. for 17 h. In addition, potassium phosphate (3.92 g, 32.4 mmol) was added there, and the mixture was stirred at the same temperature for 27 h. After reaction mixture was cooled at room temperature, it was diluted with water to give a solid. The solid was collected by filtration, and it was washed with 300 mL of MeOH. The crude product was purified by by column chromatography on silica gel eluting with CH.sub.2Cl.sub.2 to yield 4.7 g (78%) of compound (B-29) as a white solid. LC-MS (m/z) 745.

Comparative Application Example 1

[0393] A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode used as an anode is first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate is exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO. The cleaned substrate is mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below are applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 Å/sec at about 10.sup.−6-10.sup.−8 mbar. As a hole injection layer, compound

##STR00238##

with 30 nm thickness is applied. Then compound

##STR00239##

with 60 nm thickness is applied as a hole transporting layer. As an exciton and electron blocker, compound

##STR00240##

for preparation, see Ir complex (7) in the application WO2005/019373) is then applied with a thickness of 10 nm.

[0394] Subsequently, a mixture of 20% by weight of emitter compound,

##STR00241##

15% by weight of compound (HTM-1) and 65% by weight of host

##STR00242##

are applied by vapor deposition in a thickness of 40 nm. Subsequently, material (V-1) is applied by vapour deposition with a thickness of 5 nm as an exciton and hole blocker.

[0395] Thereafter, compound

##STR00243##

with 20 nm thickness is deposited as an electron transport layer. Finally, 1 nm-thick LiF is deposited as an electron injection layer and 80 nm-thick Al is then deposited as a cathode to complete the device. The device is sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen

[0396] OLED Characterization

[0397] To characterize the OLED, electroluminescence spectra are recorded at various currents and voltages. In addition, the current-voltage characteristic is measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U and EQE are given at luminance (L)=1000 cd/m.sup.2. Furthermore, 50% lifetime (LT50), the time spent until the initial luminance of 40'000 cd/m.sup.2 is reduced to 50% (2'000 cd/m.sup.2), is recorded. EQE and LT50 of the Comparative Application Examples are set to 100 and EQE and LT50 of the Application Examples are specified in relation to those of the Comparative Application Examples.

Application Examples 1 and 2

[0398] Comparative Application Example 1 is repeated except that the host (V-1) and the exciton and hole blocker (V-1) are replaced by compound

##STR00244##

and

##STR00245##

respectively. The device results are shown in Table 1.

TABLE-US-00001 TABLE 1 LT50 [%] Appl. Ex. Host HBL U [V] EQE [%] @4k nit 1 (B-50) (B-50) 5.16 95 172 2 (B-49) (B-49) 5.25 96 200 Comp. Appl. Ex. 1 (V-1)  .sup. (SH-1) 4.89 100 100

[0399] As shown in Table 1, it is found that the LT50 is improved by replacing the reference compound (V-1) with the compound (B-49) and (B-50), respectively as a host.

Comparative Application Example 2

[0400] Comparative Application Example 1 is repeated except that the exciton and hole blocker (V-1) is replaced by compound

##STR00246##

Application Examples 3 and 4

[0401] Comparative Application Example 2 is repeated except that the host (V-1) is replaced by compound (B-50) and (B-49), respectively. The device results are shown in Table 2.

TABLE-US-00002 TABLE 2 LT50 [%] Appl. Ex. Host HBL U [V] EQE [%] @4k nit 3 (B-50) (SH-1) 5.36 95 168 4 (B-49) (SH-1) 5.67 96 208 Comp. Appl. Ex. 2 (V-1)  (SH-1) 4.98 100 100

[0402] As shown in Table 2, it is found that the LT50 is improved by replacing the reference compound (V-1) with the compound (B-50) and (B-49), respectively as host.