Benzimidazo[1,2-A]benzimidazole derivatives for electronic applications

1. A process for the preparation of a compound of formula

comprising halogenating a compound of formula

wherein

X 3 is Cl, Br, or I;

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of H; a C 1 -C 25 alkyl group, which can optionally be substituted by E and/or interrupted by D; a C 6 -C 24 aryl group, which can optionally be substituted by G; and a C 2 -C 30 heteroaryl group, which can optionally be substituted by G;

X 1 is a group of formula -(A 1 ) o -(A 2 ) p -(A 3 ) q -(A 4 ) r -R 16′ ;

o is 0 or 1, p is 0 or 1, q is 0 or 1, r is 0 or 1,

A 1 , A 2 , A 3 and A 4 are independently selected from the group consisting of a C 6 -C 24 arylen group, which can optionally be substituted by G, and a C 2 -C 30 heteroarylen group, which can optionally be substituted by G; wherein

the groups A 1 , A 2 , A 3 and A 4 may be interrupted by a group —(SiR 17 R 18 )—;

R 16′ is a C 6 -C 24 aryl group, which can optionally be substituted by G; or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G;

R 17 and R 18 are independently selected from the group consisting of a C 1 -C 25 alkyl group, and a C 6 -C 24 aryl group, which can optionally be substituted by a C 1 -C 25 alkyl group;

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; a C 1 -C 18 alkyl group; a C 6 -C 24 aryl group; a C 6 -C 24 aryl group, which is substituted by F, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by O; a C 2 -C 30 heteroaryl group; or a C 2 -C 30 heteroaryl group, which is substituted by F, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by O;

R 63 and R 64 are independently selected from the group consisting of 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; and C 1 -C 18 alkyl which is interrupted by —O—;

R 65 and R 66 are independently selected from the group consisting of a C 6 -C 18 aryl group; a C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; and a C 1 -C 18 alkyl group, which is interrupted by —O—; or

R 65 and R 66 together form a five or six membered ring,

R 67 is a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—,

R 68 is H; a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—,

R 69 is a C 6 -C 18 aryl; a C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—,

R 70 and R 71 are independently selected from the group consisting of a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group, and a C 6 -C 18 aryl group, which is substituted by C 1 -C 18 alkyl, and

R 72 is a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group, or a C 6 -C 18 aryl group, which is substituted by C 1 -C 18 alkyl.

2. A compound of formula

wherein

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of H; a C 1 -C 25 alkyl group, which can optionally be substituted by E and/or interrupted by D; a C 6 -C 24 aryl group, which can optionally be substituted by G; and a C 2 -C 30 heteroaryl group, which can optionally be substituted by G;

X 1 is a group of formula -(A 1 ) o -(A 2 ) p -(A 3 ) q -(A 4 ) r -R 16″ ,

o is 0 or 1, p is 0 or 1, q is 0 or 1, r is 0 or 1,

or is a group of the formula A 1 -(A 2 ) p -(A 3 ) q -(A 4 ) r -R 16″ ,

X 3 is a group of formula -(A 5 ) v -(A 6 ) s -(A 7 ) t -(A 8 ) u -R 15′ , wherein v is 0 or 1, s is 0 or 1, t is 0 or 1, u is 0 or 1, wherein R 15′ and R 16″ are independently selected from the group consisting of Cl; Br; I; ZnX 12 , wherein X 12 is a halogen atom; —SnR 207 R 208 R 209 ; wherein R 207 , R 208 and R 209 are identical or different and are H or C 1 -C 8 alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched; —B(OH) 2 ; —B(OY 1 ) 2 ;

—BF 4 Na; and —BF 4 K, wherein each Y 1 is independently a C 1 -C 18 alkyl group and each Y 2 is independently in each occurrence a C 2 -C 10 alkylene group, and Y 13 and Y 14 are independently selected from the group consisting of hydrogen and a C 1 -C 18 alkyl group,

A 1 , A 2 , A 3 and A 4 are independently selected from the group consisting of a C 6 -C 24 arylen group, which can optionally be substituted by G, and a C 2 -C 30 heteroarylen group, which can optionally be substituted by G; wherein

the groups A 1 , A 2 , A 3 and A 4 may be interrupted by a group —(SiR 17 R 18 )—;

A 5 , A 6 , A 7 and A 8 are independently selected from the group consisting of a C 6 -C 24 arylen group, which can optionally be substituted by G, and a C 2 -C 30 heteroarylen group, which can optionally be substituted by G; wherein

the groups A 5 , A 6 , A 7 and A 8 may be interrupted by a group —(SiR 17 R 18 )—;

R 16′ is a C 6 -C 24 aryl group, which can optionally be substituted by G; or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G;

R 17 and R 18 are independently selected from the group consisting of a C 1 -C 25 alkyl group, and a C 6 -C 24 aryl group, which can optionally be substituted by a C 1 -C 25 alkyl group;

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; a C 1 -C 18 alkyl group; a C 6 -C 24 aryl group; a C 6 -C 24 aryl group, which is substituted by F, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by 0; a C 2 -C 30 heteroaryl group; or a C 2 -C 30 heteroaryl group, which is substituted by F, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by O;

R 63 and R 64 are independently selected from the group consisting of 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; and C 1 -C 18 alkyl which is interrupted by —O—;

R 65 and R 66 are independently selected from the group consisting of a C 6 -C 18 aryl group; a C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; and a C 1 -C 18 alkyl group, which is interrupted by —O—; or

R 65 and R 66 together form a five or six membered ring, R 67 is a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—,

R 68 is H; a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—,

R 69 is a C 6 -C 18 aryl; a C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—,

R 70 and R 71 are independently selected from the group consisting of a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group, and a C 6 -C 18 aryl group, which is substituted by C 1 -C 18 alkyl, and

R 72 is a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group, or a C 6 -C 18 aryl group, which is substituted by C 1 -C 18 alkyl.

3. The compound according to claim 2 , which is a compound of the formula

wherein X 1 and X 3 are as defined in claim 2 .

4. The compound according to claim 2 , wherein X 1 is

5. The compound according to claim 2 , wherein the compound of formula (II) is selected from the group consisting of:

and