Bispyrimidines for electronic applications
The present invention relates to compounds of formula a process for their production and their use in electronic devices, especially electroluminescent devices. When used as electron transport material in electroluminescent devices, the compounds of formula I, or II may provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent devices.
1. A compound of the formula
wherein
Ar 1 , Ar 2 , Ar 1′ and Ar 2′ are independently of each other a C 6 -C 24 aryl group, or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G, a C 4 -C 18 cycloalkyl group, a C 6 -C 10 aryl group, a C 6 -C 10 aryl group which is substituted by a C 1 -C 8 alkyl group, a C 2 -C 5 heteroaryl group, or a C 2 -C 5 heteroaryl group, which is substituted by a C 1 -C 8 alkyl group,
R 1 and R 2 can be the same or different at each occurrence and are F, CN, NR 45 R 45′ , a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, a C 1 -C 25 alkoxy group which is substituted by E or interrupted by D, a C 6 -C 24 aryl group, a C 6 -C 24 aryl group which is substituted by G, a C 2 -C 30 heteroaryl group, a C 2 -C 30 heteroaryl group, which is substituted by G,
m and n are 0, 1, 2, 3, or 4,
D is —CO—, —COO—, —S—, —SO—, —SO 2 —, —O—, —NR 65 —, —SiR 70 R 71 —, —POR 72 —, —CR 63 ═CR 64 —, or —C≡C—,
E is —OR 69 , —SR 69 , —NR 65 R 66 , —COR 68 , —COOR 67 , —CONR 65 R 66 , —CN, or halogen,
G is E, or C 1 -C 25 alkyl,
R 45 and R 45′ are independently of each other a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, in which one or more carbon atoms which are not in neighborhood to each other could be replaced by —NR 45″ —, —O—, —S—, —C(═O)—O—, or, —O—C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R 1 , and
R 45″ is a C 1 -C 25 alkyl group, or a C 4 -C 18 cycloalkyl group,
R 63 and R 64 are independently of each other H, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—;
R 65 and R 66 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—; or R 65 and R 66 together form a five or six membered ring, or ring system;
R 67 is C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 68 is H; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 69 is C 6 -C 18 aryl; C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 70 and R 71 are independently of each other C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, and
R 72 is C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl.
2. The compound of formula II according to claim 1 , which is a compound of formula
wherein Ar 1 , Ar 2 , Ar 1′ and Ar 2′ are as defined in claim 1 .
3. The compound according to claim 2 , wherein Ar 1 , Ar 2 , Ar 1′ and Ar 2′ are independently of each other selected from
4. The compound according to claim 3 :
Cpd.
Ar 1 = Ar 1′
Ar 2 = Ar 2′
A-1
A-2
A-3
A-4
A-5
A-6
A-7
A-8
5. The compound of formula I according to claim 1 , which is a compound of formula
wherein Ar 1 , Ar 2 , Ar 1′ and Ar 2′ are as defined in claim 1 .
6. The compound according to claim 5 , wherein Ar 1 , Ar 2 , Ar 1′ and Ar 2′ are independently of each other selected from
7. The compound according to claim 6 :
Cpd.
Ar 1 = Ar 1′
Ar 2 = Ar 2′
B-1
B-2
B-3
B-4
B-5
B-6
B-7
B-8
8. An electronic device, comprising a compound according to any of claims 1 to 7 .
9. The electronic device according to claim 8 , which is an electroluminescent device.
10. An electron transport layer, comprising a compound according to any of claims 1 to 7 .
11. An apparatus selected from the group consisting of stationary visual display units, illuminations, information panels, and mobile visual display units comprising the organic electronic device according to claim 8 .
12. A process for the preparation of compounds of the formula
which comprises reacting a compound of formula
wherein X 11 stands for halogen, with a compound of formula
wherein X 12 is —B(OH) 2 , —B(OY 1 ) 2 ,
wherein Y 1 is independently in each occurrence a C 1 -C 18 alkyl group and Y 2 is independently in each occurrence a C 2 -C 10 alkylene group and Y 13 and Y 14 are independently of each other hydrogen, or a C 1 -C 18 alkyl group, in the presence of a base and a catalyst in a solvent,
wherein Ar 1 , Ar 1′ , Ar 2 , Ar 2′ , m, n, R 1 and R 2 are as defined in claim 1 .
13. A process for the preparation of compounds of the formula
which comprises reacting a compound of formula
wherein X 11 stands for halogen, with a compound of formula
wherein X 12 is —B(OH) 2 , —B(OY 1 ) 2 ,
wherein Y 1 is independently in each occurrence a C 1 -C 18 alkyl group and Y 2 is independently in each occurrence a C 2 -C 10 alkylene group, and Y 13 and Y 14 are independently of each other hydrogen, or a C 1 -C 18 alkyl group, in the presence of a base and a catalyst in a solvent,
wherein Ar 1 , Ar 1′ , Ar 2 , Ar 2′ , m, n, R 1 and R 2 are as defined in claim 1 .
14. The process according to claim 12 , wherein Y 2 is CY 3 Y 4 —CY 5 Y 6 —, or —CY 7 Y 8 —CY 9 Y 10 —CY 11 Y 12 —, wherein Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 are independently of each other hydrogen, or a C 1 -C 18 alkyl group.
15. The process according to claim 12 , wherein Y 2 is —C(CH 3 ) 2 C(CH 3 ) 2 —, —C(CH 3 ) 2 CH 2 C(CH 3 ) 2 — or —CH 2 C(CH 3 ) 2 CH 2 —.
16. The process according to claim 13 , wherein Y 2 is CY 3 Y 4 —CY 5 Y 6 —, or —CY 7 Y 8 —CY 9 Y 10 —CY 11 Y 12 —, wherein Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 are independently of each other hydrogen, or a C 1 -C 18 alkyl group.
17. The process according to claim 13 , wherein Y 2 is —C(CH 3 ) 2 C(CH 3 ) 2 —, —C(CH 3 ) 2 CH 2 C(CH 3 ) 2 — or —CH 2 C(CH 3 ) 2 CH 2 —.
18. The apparatus according to claim 11 , wherein said apparatus is a stationary visual display unit selected from the group consisting of a visual display unit of a computer, a visual display unit of a television, a visual display unit of a printer, a kitchen appliance and an advertising panel.
19. The apparatus according to claim 11 , wherein said apparatus is a mobile visual display unit selected from the group consisting of a cellphone visual display unit , a laptop visual display unit, a digital camera visual display unit, an MP3 player visual display unit, a bus vehicle and destination display, a train vehicle and destination display, an illumination unit; a keyboard; an item of clothing; furniture and wallpaper.