HETEROAROMATIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to heteroaromatic compounds suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Claims

1.-15. (canceled)

16. A compound comprising at least one structure having at least three mutually fused structural elements of the formulae (A), (B) and (C): ##STR00575## where structural element (A) is fused to structural element (B) and structural element (B) is fused to structural element (C); where structural element (B) binds to structural element (A) via the bonds shown by dotted lines, where there is one bond via the binding site marked # and one bond via a binding site marked *; where structural element (B) is fused to structural element (C) via the atoms marked o and +, and the respectively marked atoms are shared by structural elements (B) and (C), and the symbols and indices used are as follows: W is O or S; Z.sup.1 is NAr, or N if structural element (A) is fused to structural element (B) via Z.sup.1; Z.sup.2 is X, or C if structural element (A) is fused to structural element (B) via Z.sup.2; Z.sup.3, Z.sup.4 is N or C, where one of the Z.sup.3, Z.sup.4 radicals is N and one of the Z.sup.3, Z.sup.4 radicals is C; X is N or CR; X.sup.1 is the same or different at each instance and is N or CR.sup.1, with the proviso that not more than two of the X.sup.1 groups in one cycle are N; X.sup.2 is the same or different at each instance and is N or CR.sup.2, with the proviso that not more than two of the X.sup.2 groups in one cycle are N; X.sup.3 is the same or different at each instance and is N or CR.sup.3, with the proviso that not more than two of the X.sup.3 groups in one cycle are N; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R radicals; R is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is possible here for two R radicals or one R radical together with a further radical to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.1 radicals or one R.sup.1 radical together with a further radical, or an R, R.sup.2, R.sup.3 group, to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.2 radicals or one R.sup.2 radical together with a further radical to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.3 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.3 radicals or one R.sup.3 radical together with a further radical to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R.sup.4 radicals; R.sup.4 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.5C?C(R.sup.5).sub.2, N(R.sup.5).sub.2, CN, NO.sub.2, OR.sup.5, SR.sup.5, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, C(?O)R.sup.5, P(?O)(R.sup.5).sub.2, S(?O)R.sup.5, S(?O).sub.2R.sup.5, OSO.sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.5 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.5C?CR.sup.5, C?C, Si(R.sup.5).sub.2, C?O, C?S, C?Se, C?NR.sup.5, C(?O)O, C(?O)NR.sup.5, NR.sup.5, P(?O)(R.sup.5), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and in each case has R.sup.5 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.5 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.5 radicals; it is possible here for two or more R.sup.4 radicals together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.5 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in which one or more hydrogen atoms may also be replaced by F; it is possible here for two or more R.sup.5 radicals together to form a ring system; where at least one of the R, R.sup.1, R.sup.2, R.sup.3 radicals is selected from the group consisting of a heteroaromatic ring system which has 6 to 60 aromatic ring atoms and has R.sup.4 radicals, an aromatic ring system which has 10 to 60 aromatic ring atoms and has R.sup.4 radicals, an aryloxy group having 10 to 60 aromatic ring atoms or heteroaryloxy group having 6 to 40 aromatic ring atoms, each of which has R.sup.4 radicals, a diarylamino group having 6 to 60 aromatic ring atoms in the respective aromatic radical, an arylheteroarylamino group having 6 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, and a diheteroarylamino group having 6 to 60 aromatic ring atoms in the respective heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals.

17. The compound as claimed in claim 16, wherein the compound comprising at least one structure of the formulae (I-1) to (I-7): ##STR00576## ##STR00577## where symbols W, X, X.sup.1, X.sup.2, X.sup.3 and Ar have the definitions given in claim 16.

18. The compound as claimed in claim 16, wherein the compound comprising at least one structure of the formulae (II-1) to (II-30): ##STR00578## ##STR00579## ##STR00580## ##STR00581## ##STR00582## ##STR00583## where the symbols X.sup.1, X.sup.2, X.sup.3, R, R.sup.1, R.sup.2, R.sup.3 and Ar have the definitions given in claim 16 and the index m is 0, 1, 2, 3 or 4.

19. The compound as claimed in claim 18, wherein the structure is of the formulae (II-1) to (II-7), (II-11) to (II-17) and/or (II-21) to (II-27).

20. The compound as claimed in claim 16, wherein the compound comprising at least one structure of the formulae (III-1) to (III-10): ##STR00584## ##STR00585## where the symbols R, R.sup.1, R.sup.2, R.sup.3 and Ar have the definitions given in claim 16 and the index m is 0, 1, 2, 3 or 4.

21. The compound as claimed in claim 16, wherein at least one R, R.sup.1, R.sup.2 and/or R.sup.3 group is the same or different and is selected from the radicals of the following formulae SAr-1 to SAr-18: ##STR00586## ##STR00587## ##STR00588## where R.sup.4 and Ar have the definitions given in claim 16 and the further symbols and indices are as follows: X.sup.4 is the same or different at each instance and is CR.sup.4, N, or C if the [Ar.sup.1].sub.p group binds thereto; X.sup.5 is the same or different at each instance and is CR.sup.4 or N; Ar.sup.1 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms and in each case has R.sup.4 radicals; Y.sup.1 is the same or different at each instance and is C(R.sup.4).sub.2, NR.sup.4, O, S, or N if the [Ar.sup.1].sub.p group binds thereto; p is 0 or 1, where p=0 means that the Ar.sup.1 group is absent and that the corresponding aromatic or heteroaromatic group is bonded directly to the corresponding radical; n is 0, 1, 2 or 3; m is 0, 1, 2, 3 or 4; l is 0, 1, 2, 3, 4 or 5; and r is 0, 1, 2, 3, 4, 5 or 6.

22. The compound as claimed in claim 16, wherein R, R.sup.1, R.sup.2 and/or R.sup.3 are the same or different at each instance and are selected from the group consisting of H, D or an aromatic or heteroaromatic ring system selected from the groups of the following formulae Ar-1 to Ar-79: ##STR00589## ##STR00590## ##STR00591## ##STR00592## ##STR00593## ##STR00594## ##STR00595## ##STR00596## ##STR00597## ##STR00598## ##STR00599## ##STR00600## ##STR00601## ##STR00602## where R.sup.4 has the definitions given above, the dotted bond represents the bond to the corresponding group and in addition: Ar.sup.1 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms and in each case has R.sup.4 radicals; A is the same or different at each instance and is C(R.sup.4).sub.2, NR.sup.4, O or S; p is 0 or 1, where p=0 means that the Ar.sup.1 group is absent and that the corresponding aromatic or heteroaromatic group is bonded directly to the corresponding radical; and q is 0 or 1, where q=0 means that no A group is bonded at this position and R.sup.4 radicals are bonded to the corresponding carbon atoms instead.

23. A process for preparing the compound as claimed in claim 16, comprising reacting a nitrogen-containing aromatic or heteroaromatic compound in a ring-forming reaction.

24. A composition comprising at least one compound comprising at least one structure having at least three mutually fused structural elements of the formulae (A), (B) and (C): ##STR00603## where structural element (A) is fused to structural element (B) and structural element (B) is fused to structural element (C); where structural element (B) binds to structural element (A) via the bonds shown by dotted lines, where there is one bond via the binding site marked # and one bond via a binding site marked *; where structural element (B) is fused to structural element (C) via the atoms marked o and +, and the respectively marked atoms are shared by structural elements (B) and (C), and the symbols and indices used are as follows: W is O or S; Z.sup.1 is NAr, or N if structural element (A) is fused to structural element (B) via Z.sup.1; Z.sup.2 is X, or C if structural element (A) is fused to structural element (B) via Z.sup.2; Z.sup.3, Z.sup.4 is N or C, where one of the Z.sup.3, Z.sup.4 radicals is N and one of the Z.sup.3, Z.sup.4 radicals is C; X is N or CR; X.sup.1 is the same or different at each instance and is N or CR.sup.1, with the proviso that not more than two of the X.sup.1 groups in one cycle are N; X.sup.2 is the same or different at each instance and is N or CR.sup.2, with the proviso that not more than two of the X.sup.2 groups in one cycle are N; X.sup.3 is the same or different at each instance and is N or CR.sup.3, with the proviso that not more than two of the X.sup.3 groups in one cycle are N; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R radicals; R is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is possible here for one R radical together with a further radical to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.1 radicals or one R.sup.1 radical together with a further radical to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.2 radicals or one R.sup.2 radical together with a further radical to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.3 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.3 radicals or one R.sup.3 radical together with a further radical; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R.sup.4 radicals; R.sup.4 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.5C?C(R.sup.5).sub.2, N(R.sup.5).sub.2, CN, NO.sub.2, OR.sup.5, SR.sup.5, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, C(?O)R.sup.5, P(?O)(R.sup.5).sub.2, S(?O)R.sup.5, S(?O).sub.2R.sup.5, OSO.sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.5 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.5C?CR.sup.5, C?C, Si(R.sup.5).sub.2, C?O, C?S, C?Se, C?NR.sup.5, C(?O)O, C(?O)NR.sup.5, NR.sup.5, P(?O)(R.sup.5), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and in each case has R.sup.5 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.5 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.5 radicals; it is possible here for two or more R.sup.4 radicals together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.5 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; it is possible here for two or more R.sup.5 radicals together to form a ring system; and at least one further matrix material, where the further matrix material is selected from compounds of at least one of the formulae (H-1), (H-2), (H-3), (H-4) and (H-5): ##STR00604## where the symbols and indices used are as follows: R.sup.6 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.7).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.7, SR.sup.7, COOR.sup.7, C(?O)N(R.sup.7).sub.2, Si(R.sup.7).sub.3, B(OR.sup.7).sub.2, C(?O)R.sup.7, P(?O)(R.sup.7).sub.2, S(?O)R.sup.7, S(?O).sub.2R.sup.7, OSO.sub.2R.sup.7, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where each alkyl, alkenyl or alkynyl group has R.sup.7 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.7).sub.2, C?O, NR.sup.7, O, S or CONR.sup.7, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.7 radicals; at the same time, two R.sup.6 radicals together may also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R.sup.7 radicals; A.sup.1 is C(R.sup.7).sub.2, NR.sup.7, O or S; Ar.sup.5 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R.sup.7 radicals; R.sup.7 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R).sub.2, CN, NO.sub.2, OR.sup.8, SR.sup.8, Si(R.sup.8).sub.3, B(OR.sup.8).sub.2, C(?O)R.sup.8, P(?O)(R.sup.8).sub.2, S(?O)R.sup.8, S(?O).sub.2R.sup.8, OSO.sub.2R.sup.8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where each alkyl, alkenyl or alkynyl group has R.sup.8 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.8).sub.2, C?O, NR.sup.8, O, S or CONR.sup.8, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and in each case has R.sup.8 radicals; at the same time, two or more R.sup.7 radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.8 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; v is the same or different at each instance and is 0, 1, 2, 3 or 4; t is the same or different at each instance and is 0, 1, 2 or 3; and u is the same or different at each instance and is 0, 1 or 2.

25. The composition as claimed in claim 24, wherein the composition consists of at least one compound containing at least one compound comprising at least one structure having at least three mutually fused structural elements of the formulae (A), (B) and (C), and at least one compound of one of the formulae (H-1), (H-2), (H-3), (H-4) and (H-5).

26. The composition as claimed in claim 24, wherein the compounds of one of the formulae (H-1), (H-2), (H-3), (H-4) and (H-5) have a proportion by mass in the composition in the range from 5% by weight to 90% by weight, based on the overall composition.

27. The composition as claimed in claim 24, wherein the compounds of one of the formulae (H-1), (H-2), (H-3), (H-4) and (H-5) have a proportion by mass in the composition in the range from 30% by weight to 50% by weight, based on the overall composition.

28. A formulation comprising at least one compound as claimed in claim 16 and at least one further compound.

29. A formulation comprising at least one composition as claimed in claim 24 and at least one further compound.

30. A formulation comprising at least one composition as claimed in claim 24 and at least one or more solvents.

31. A formulation comprising at least one compound as claimed in claim 16 and at least one or more solvents.

32. An electronic device containing at least one compound comprising at least one structure having at least three mutually fused structural elements of the formulae (A), (B) and (C): ##STR00605## where structural element (A) is fused to structural element (B) and structural element (B) is fused to structural element (C); where structural element (B) binds to structural element (A) via the bonds shown by dotted lines, where there is one bond via the binding site marked # and one bond via a binding site marked *; where structural element (B) is fused to structural element (C) via the atoms marked o and +, and the respectively marked atoms are shared by structural elements (B) and (C), wherein W is O or S; Z.sup.1 is NAr, or N if structural element (A) is fused to structural element (B) via Z.sup.1; Z.sup.2 is X, or C if structural element (A) is fused to structural element (B) via Z.sup.2; Z.sup.3, Z.sup.4 is N or C, where one of the Z.sup.3, Z.sup.4 radicals is N and one of the Z.sup.3, Z.sup.4 radicals is C; X is N or CR; X.sup.1 is the same or different at each instance and is N or CR.sup.1, with the proviso that not more than two of the X.sup.1 groups in one cycle are N; X.sup.2 is the same or different at each instance and is N or CR.sup.2, with the proviso that not more than two of the X.sup.2 groups in one cycle are N; X.sup.3 is the same or different at each instance and is N or CR.sup.3, with the proviso that not more than two of the X.sup.3 groups in one cycle are N; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R radicals; R is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is possible here for one R radical together with a further radical to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.1 radicals or one R.sup.1 radical together with a further radical to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.2 radicals or one R.sup.2 radical together with a further radical to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.3 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.4C?C(R.sup.4).sub.2, N(R.sup.4).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.4, OAr, SR.sup.4, SAr, C(?O)OR.sup.4, C(?O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(?O)R.sup.4, P(?O)(R.sup.4).sub.2, S(?O)R.sup.4, S(?O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C?CR.sup.4, C?C, Si(R.sup.4).sub.2, C?O, C?S, C?Se, C?NR.sup.4, C(?O)O, C(?O)NR.sup.4, NR.sup.4, P(?O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.4 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.4 radicals; it is also possible here for two R.sup.3 radicals or one R.sup.3 radical together with a further radical; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R.sup.4 radicals; R.sup.4 is the same or different at each instance and is H, D, F, Cl, Br, I, R.sup.5C?C(R.sup.5).sub.2, N(R.sup.5).sub.2, CN, NO.sub.2, OR.sup.5, SR.sup.5, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, C(?O)R.sup.5, P(?O)(R.sup.5).sub.2, S(?O)R.sup.5, S(?O).sub.2R.sup.5, OSO.sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, where each alkyl, alkoxy or thioalkyl, alkenyl or alkynyl group has R.sup.5 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.5C?CR.sup.5, C?C, Si(R.sup.5).sub.2, C?O, C?S, C?Se, C?NR.sup.5, C(?O)O, C(?O)NR.sup.5, NR.sup.5, P(?O)(R.sup.5), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and in each case has R.sup.5 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and in each case has R.sup.5 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms in the respective aromatic or heteroaromatic radical, where the diarylamino, arylheteroarylamino, diheteroarylamino group has R.sup.5 radicals; it is possible here for two or more R.sup.4 radicals together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.5 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; it is possible here for two or more R.sup.5 radicals together to form a ring system

33. The electronic device as claimed in claim 32, wherein the device is an organic electroluminescent device.

34. The electronic device as claimed in claim 32 which is an organic electroluminescent device, wherein the compound comprising at least one structure having at least three mutually fused structural elements of the formulae (A), (B) and (C) is used as matrix material in an emitting layer and/or in an electron transport layer and/or in a hole blocker layer.

35. The electronic device as claimed in claim 32, wherein the compound comprising at least one structure having at least three mutually fused structural elements of the formulae (A), (B) and (C), is used as matrix material for phosphorescent emitters in combination with a further matrix material selected from compounds of one of the formulae (H-1), (H-2), (H-3), (H-4) and (H-5), ##STR00606## where the symbols and indices used are as follows: R.sup.6 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.7).sub.2, N(Ar).sub.2, CN, NO.sub.2, OR.sup.7, SR.sup.7, COOR.sup.7, C(?O)N(R.sup.7).sub.2, Si(R.sup.7).sub.3, B(OR.sup.7).sub.2, C(?O)R.sup.7, P(?O)(R.sup.7).sub.2, S(?O)R.sup.7, S(?O).sub.2R.sup.7, OSO.sub.2R.sup.7, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where each alkyl, alkenyl or alkynyl group has R.sup.7 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.7).sub.2, C?O, NR.sup.7, O, S or CONR.sup.7, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and in each case has R.sup.7 radicals; at the same time, two R.sup.6 radicals together may also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R.sup.7 radicals; A.sup.1 is C(R.sup.7).sub.2, NR.sup.7, 0 or S; Ar.sup.5 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and has R.sup.7 radicals; R.sup.7 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R).sub.2, CN, NO.sub.2, OR.sup.8, SR.sup.8, Si(R.sup.8).sub.3, B(OR.sup.8).sub.2, C(?O)R.sup.8, P(?O)(R.sup.8).sub.2, S(?O)R.sup.8, S(?O).sub.2R.sup.8, OSO.sub.2R.sup.8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where each alkyl, alkenyl or alkynyl group has R.sup.8 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.8).sub.2, C?O, NR.sup.8, O, S or CONR.sup.8, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and in each case has R.sup.8 radicals; at the same time, two or more R.sup.7 radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.8 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; v is the same or different at each instance and is 0, 1, 2, 3 or 4; t is the same or different at each instance and is 0, 1, 2 or 3; and u is the same or different at each instance and is 0, 1 or 2.

Description

EXAMPLES

[0186] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. For the compounds known from the literature, the corresponding CAS numbers are also reported in each case.

SYNTHESIS EXAMPLES

a) 2-(2-Fluorophenyl)-3-methylisoquinolin-1-one

[0187] ##STR00431##

[0188] 6.3 g (40 mmol) of 3-methyl-1(2H)-isoquinolinone and 9.9 g (45 mmol) of 1-fluoro-2-iodobenzene and 44.7 g (320 mmol) of potassium carbonate, 3 g (16 mmol) of copper(I) iodide and 3.6 g (16 mmol) of 1,3-di(pyridin-2-yl)propane-1,3-dione are stirred in 100 ml of DMF at 150? C. for 30 h. The solution is diluted with water and extracted twice with ethyl acetate, and the combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated. The residue is purified by chromatography (EtOAc/hexane: 2/3), recrystallized from toluene and finally purified under high vacuum (p=5?10.sup.?5 mbar). The purity is 99.9%. The yield is 8.1 g (30 mmol), 77% of theory.

[0189] The following compounds are prepared in an analogous manner:

TABLE-US-00003 Ex. Reactant 1 Reactant 2 Product Yield 1a [00432] [00433] [00434] 75% 2a [00435] [00436] [00437] 68% 3a [00438] [00439] [00440] 74% 4a [00441] [00442] [00443] 61% 5a [00444] [00445] [00446] 79% 6a [00447] [00448] [00449] 70% 7a [00450] [00451] [00452] 66% 8a [00453] [00454] [00455] 71%

b) 3-(2-Fluorophenyl)-4-oxoquinazoline-2-carbaldehyde

[0190] ##STR00456##

[0191] 25.4 g (100 mmol) of 2-(2-fluorophenyl)-3-methylisoquinolin-1-one is dissolved in 500 ml of hot dioxane, and then 12 g of pulverized selenium dioxide (200 mmol) is added in portions while stirring. On completion of addition, the reaction mixture is heated under reflux for 8 h. Then the reaction mixture is filtered, ice-cold water is added to the solution, and the product is filtered off and recrystallized in toluene.

[0192] The yield is 18 g (73 mmol), corresponding to 70% of theory.

[0193] The following compounds are prepared in an analogous manner:

TABLE-US-00004 Ex. Reactant 1 Product Yield 1b [00457] [00458] 65%

c) 2,6-Diphenyl-8-(2-phenylphenyl)-9H-purine

[0194] ##STR00459##

[0195] A solution of 7.5 g (28 mmol) of 3-(2-fluorophenyl)-4-oxoquinazoline-2-carbaldehyde and 3 g (28 mmol) of phenylene-1,2-diamine in 50 ml of DMF is heated to 80? C. The reaction mixture is left to stir for 8 h, and the resultant solution is brought to room temperature and then extracted with ethyl acetate (EtOAc). The organic layer is washed with salt solution, dried over anhydrous Na.sub.2SO.sub.4, and concentrated under reduced pressure. The crude product is purified by silica gel column chromatography with n-hexane-EtOAc. Yield: 7.7 (21 mmol), 78% of theory.

[0196] The following compounds can be obtained analogously:

TABLE-US-00005 Ex. Reactant 1 Reactant 2 Product Yield 1c [00460] [00461] [00462] 73% 2c [00463] [00464] [00465] 60%

d) 3-(1H-Benzimidazol-2-yl)-2-(2-fluorophenyl)quinazolin-4-one

[0197] ##STR00466##

[0198] A mixture of 4.8 g (20 mmol) of 2-(2-fluorophenyl)-3,1-benzoxazin-4-one and 2.66 g (20 mmol) of 2-aminobenzimidazole is fused together in an oil bath at 200-250? C. for 30 minutes, in such a way that the reaction mixture is not to evaporate off owing to high heating. The mixture is cooled down, 20 ml of ethanol is added, and the mixture is filtered. The solids separated off are washed with ethanol, dried and recrystallized repeatedly with ethanol in order to obtain the pure product. Yield: 4.6 (13 mmol), 65% of theory.

[0199] The following compounds can be obtained analogously:

TABLE-US-00006 Ex. Reactant 1 Reactant 2 Product Yield 1d [00467] [00468] [00469] 57% 2d [00470] [00471] [00472] 61% 3d [00473] [00474] [00475] 60% 4d [00476] [00477] [00478] 53%

e) Cyclization

[0200] ##STR00479##

[0201] To a solution of 1.78 g (5 mmol) of 2,6-diphenyl-8-(2-phenylphenyl)-9H-purine in 50 ml of DMF is added 0.32 g (1 mmol) of Cs.sub.2CO.sub.3, and the reaction mixture is heated at 150? C. in a microwave for 10 min. Once the microwave vial has cooled down to room temperature, the solvent is diluted with EtOAc (150 ml) and washed with saturated NaCl solution (2?100 ml). The organic phase is separated and dried over Mg.sub.2SO.sub.4. The residue is purified by column chromatography using an ethyl acetate/hexane gradient (0-60%). The residue is recrystallized from toluene and finally under high vacuum (p=5?10.sup.?5 mbar). The purity is 99.9%.

[0202] Yield: 1.3 (3.9 mmol), 78% of theory.

[0203] The following compounds can be obtained analogously:

TABLE-US-00007 Ex. Reactant 1 Product Yield 1e [00480] [00481] 69% 2e [00482] [00483] 74% 3e [00484] [00485] 71% 4e [00486] [00487] 68%

f) Cyclization

[0204] ##STR00488##

[0205] A mixture of 2 g (7.5 mmol) of 6-(methylthio)benzimidazo[1,2-c]quinazoline, 3.74 g (43 mmol) of anthranilic acid and 20 g of graphite in a 70 ml quartz vial is introduced into a microwave oven. Irradiation is programmed at 105 W for 90 min. After a period of 2?3 min., the mixture reaches 170? C. and stays constant at that temperature. After cooling, the graphite powder is filtered, reacted with 10 ml of dichloromethane, filtered, and washed with 5 ml of dichloromethane. The organic solution is washed with a saturated sodium bicarbonate solution, and the crude product is recrystallized in ethanol.

[0206] Yield: 3.0 g (6.64 mmol), 88% of theory.

[0207] The following compounds can be obtained analogously:

TABLE-US-00008 Ex. Reactant 1 Reactant 2 Product Yield 1f [00489] [00490] [00491] 89% 2f [00492] [00493] [00494] 87% 3f [00495] [00496] [00497] 64% 4f [00498] [00499] [00500] 61% 5f [00501] [00502] [00503] 72% 6f [00504] [00505] [00506] 70% 7f [00507] [00508] [00509] 58%

g) Cyclization

[0208] ##STR00510##

[0209] Under protective gas, 3.9 g (20 mmol, 1.0 eq.) of 2-phenylbenzimidazole, 14.1 g (30 mmol, 1.5 eq.) of 3,4-diiodo-2-phenyl-1(2H)-isoquinolinone and 8.2 g (60 mmol, 3.0 eq.) of K.sub.2CO.sub.3, 0.5 (2 mmol) of Pd(OAc).sub.2 and finally 1.9 g (4 mmol) of Xphos are added to 200 ml of DMF. The mixture is heated at 160? C. for 80 h and then comes to room temperature. This is followed by quenching for 5 min with water and dilution with 8 ml of ethyl acetate. The organic phase is separated and concentrated under reduced pressure. The crude product is then separated by flash chromatography on silica gel (3-10% ethyl acetate/petroleum ether).

[0210] Yield: 2.9 g (18.9 mmol), 63% of theory

[0211] The following compounds can be obtained analogously:

TABLE-US-00009 Ex. Reactant 1 Reactant 2 Product Yield 1g [00511] [00512] [00513] 32% 2g [00514] [00515] [00516] 37% 3g [00517] [00518] [00519] 41% 4g [00520] [00521] [00522] 55%

h) 3-(2-Bromophenyl)-1-oxo-2H-isoquinoline-4-carbaldehyde

[0212] ##STR00523##

[0213] 9.7 g (63.6 mmol) of phosphorus oxychloride is added to 40 ml of dimethylformamide, and the mixture is cooled in an ice bath. The flask is stirred for 4 hours. The resulting mixture is stirred at the same temperature for 4 h. An ice-cold solution of 3.2 g (12.7 mmol) of 3-(2-bromophenyl)-2H-isoquinolin-1-one in DMF (10 ml) is added dropwise to the mixture and, after the addition has ended, warmed gradually to 60? C. and stirred for 20 hours. The reaction mixture is cooled in an ice bath, 50 ml of ice-cold water is added cautiously, and the mixture is basified with 35% NaOH solution. The solids are filtered off. The filtrate is extracted with ethyl acetate. The combined ethyl acetate extracts are washed with water and salt solution, dried over anhydrous sodium sulfate and then concentrated. The residue is recrystallized from methanol.

[0214] Yield: 2.8 g (8.5 mmol), 80% of theory

i) Cyclization

[0215] ##STR00524##

[0216] Under protective gas, 16.6 g (40 mmol, 1.0 eq.) of compound 1c, 16.4 g (120 mmol, 3.0 eq.) of K2C03, 1 g (4 mmol) of Pd(OAc).sub.2 and finally 3.8 g (8 mmol) of Xphos are added to 400 ml of DMF. The mixture is heated at 160? C. for 80 h and then comes to room temperature. This is followed by quenching with 20 ml of water and dilution with 20 ml of ethyl acetate. The organic phase is separated and concentrated under reduced pressure. The crude product is then separated by flash chromatography on silica gel (3-10% ethyl acetate/petroleum ether).

[0217] Yield: 8 g (22 mmol), 75% of theory

[0218] The following compounds can be obtained analogously:

TABLE-US-00010 Ex. Reactant 1 Product Yield 1i [00525] [00526] 65%

j) Suzuki Reaction

[0219] ##STR00527##

[0220] 53 g (155 mmol) of compound f, 41 g (172 mmol) of 9,9-dimethyl-9H-fluorene-2-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol diamine ether and 280 ml of water. To this suspension is added 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0), and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel and then concentrated to dryness. The product is purified via column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed under high vacuum (p=5?10.sup.?7 mbar) (99.9% purity). The yield is 42 g (80 mmol), corresponding to 70% of theory.

[0221] The following compounds are prepared in an analogous manner:

TABLE-US-00011 Ex. Reactant 1 Reactant 2 Product Yield 1j [00528] [00529] [00530] 73% 2j [00531] [00532] [00533] 84% 3j [00534] [00535] [00536] 72% 4j [00537] [00538] [00539] 79% 5j [00540] [00541] [00542] 71% 6j [00543] [00544] [00545] 69% 7j [00546] [00547] [00548] 71% 8j [00549] [00550] [00551] 80%

Production of the Electroluminescent Devices

[0222] Examples E1 to E16 which follow (see table 1) present the use of the materials of the invention in OLEDs.

[0223] Pretreatment for Examples E1 to E16: Glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plates form the substrates to which the OLEDs are applied.

[0224] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm. The exact structure of the OLEDs can be found in table 1. The materials required for production of the OLEDs are shown in table 2.

[0225] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as EG1:IC2:TEG1 (49%:44%:7%) mean here that the material EG1 is present in the layer in a proportion by volume of 49%, IC2 in a proportion of 44% and TEG1 in a proportion of 7%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0226] The OLEDs are characterized in a standard manner. For this purpose, electroluminescence spectra, current efficiency (CE, measured in cd/A) and external quantum efficiency (EQE, measured in %) are determined as a function of luminance, calculated from current-voltage-luminance characteristics assuming Lambertian emission characteristics. The parameter U1000 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and EQE1000 respectively denote the current efficiency and external quantum efficiency that are attained at 1000 cd/m.sup.2. Electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and these are used to calculate the CIE 1931 x and y color coordinates. The results thus obtained can be found in table 3.

Use of the Materials of the Invention in OLEDs

[0227] Inventive compound EG1 is used in example E1 as matrix material in the emission layer of red-phosphorescing OLEDs. Compounds EG2 to EG13 are used in examples E2 to E13 as matrix material in the emission layer of green-phosphorescing OLEDs. Inventive compounds EG3, EG7 and EG9 are used in examples E14 to E16 as electron transporter in the electron transport layer (ETL) of green-phosphorescing OLEDs.

[0228] In all cases, good performance data of the OLEDs are achieved (table 3).

TABLE-US-00012 TABLE 1 Structure of the electroluminescent devices HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness E1 HATCN SpMA1 SpMA2 EG1:IC2:TER5 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (57%:40%:7%) 5 nm (50%:50%) 1 nm 35 nm 30 nm E2 HATCN SpMA1 SpMA2 EG2:IC2:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (49%:44%:7%) 5 nm (50%:50%) 1 nm 40 nm 30 nm E3 HATCN SpMA1 SpMA2 EG3:IC2:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (49%:44%:7%) 5 nm (50%:50%) 1 nm 40 nm 30 nm E4 HATCN SpMA1 SpMA2 EG4:IC2:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (49%:44%:7%) 5 nm (50%:50%) 1 nm 40 nm 30 nm E5 HATCN SpMA1 SpMA2 EG5:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (45%:45%:10%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E6 HATCN SpMA1 SpMA2 EG6:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E7 HATCN SpMA1 SpMA2 EG7:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E8 HATCN SpMA1 SpMA2 EG8:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (46%:47%:7%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E9 HATCN SpMA1 SpMA2 EG9:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (46%:47%:7%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E10 HATCN SpMA1 SpMA2 EG10:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (46%:47%:7%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E11 HATCN SpMA1 SpMA2 EG11:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (46%:47%:7%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E12 HATCN SpMA1 SpMA2 EG12:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (46%:47%:7%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E13 HATCN SpMA1 SpMA2 EG13:IC1:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (46%:47%:7%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E14 HATCN SpMA1 SpMA2 IC1:TEG1 EG3 LiQ 5 nm 70 nm 15 nm (90%:10%) 45 nm 3 nm 25 nm E15 HATCN SpMA1 SpMA2 IC1:TEG1 EG7 LiQ 5 nm 70 nm 15 nm (90%:10%) 45 nm 3 nm 25 nm E16 HATCN SpMA1 SpMA2 IC1:TEG1 EG9 LiQ 5 nm 70 nm 15 nm (90%:10%) 45 nm 3 nm 25 nm

TABLE-US-00013 TABLE 2 Structural formulae of the materials for the electroluminescent devices [00552] [00553] [00554] [00555] [00556] [00557] [00558] [00559] [00560] [00561] [00562] [00563] [00564] [00565] [00566] [00567] [00568] [00569] [00570] [00571] [00572] [00573] [00574]

[0229] The figure between brackets for the respective compound in table 2 relates to the synthesis example.

TABLE-US-00014 TABLE 3 Performance data of the electroluminescent devices U1000 SE1000 EQE 1000 CIE x/y at Ex. (V) (cd/A) (%) 1000 cd/m.sup.2 E1 3.7 23 21 0.66/0.34 E2 4.1 67 16 0.33/0.62 E3 3.9 65 17 0.35/0.61 E4 3.7 70 16.7 0.35/0.62 E5 4.2 74 16.8 0.33/0.63 E6 4.4 63 17.0 0.33/0.62 E7 3.8 70 16.3 0.32/0.64 E8 3.6 79 17.3 0.32/0.63 E9 3.7 73 17.8 0.33/0.62 E10 3.3 75 18.8 0.33/0.63 E11 3.2 76 19.7 0.33/0.63 E12 3.2 73 19.9 0.33/0.63 E13 3.1 67 19.5 0.33/0.63 E14 3.4 64 18.8 0.33/0.62 E15 3.5 64 17.9 0.33/0.63 E16 3.3 66 18.2 0.33/0.62