COMPOUNDS FOR ELECTRONIC DEVICES

Abstract

The present invention relates to condensed N-heteroaromatic compounds, to processes for preparing these compounds, and to electronic devices containing said compounds.

Claims

1. An electronic device comprising a compound containing a structural element of the formula (I) ##STR00661## where: Z.sup.1 is the same or different at each instance and is C, CR.sup.1 or N; Z.sup.2 is the same or different at each instance and is C, CR.sup.2 or N; T.sup.1 is the same or different at each instance and is selected from (C═O)(NAr.sup.1)—, —(C═S)(NAr.sup.1)—, —(SO.sub.2)(NAr.sup.1)—, and —(C═O)O—; Ar.sup.1 is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by one or more R.sup.3 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by one or more R.sup.3 radicals; R.sup.1 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, 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; R.sup.2 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, 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; R.sup.3 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, 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; R.sup.4 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, 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; R.sup.5 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN; k is 0 or 1, where, in the case that k=1, the Z.sup.1 and Z.sup.2 groups that bind to the T.sup.1 group in question are C and are bonded to one another via the T.sup.1 group, and where, in the case that k=0, the T.sup.1 group in question is absent, and the Z.sup.1 and Z.sup.2 groups in question are not bonded to one another.

2. The electronic device as claimed in claim 1, wherein T.sup.1 is —(C═O)(NAr.sup.1)—.

3. The electronic device as claimed in claim 1, wherein Ar.sup.1 is the same or different at each instance and is selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, triphenylene, naphthyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, triazinyl, pyrimidyl, pyridyl, quinazoline, quinoxaline and quinoline, where the groups mentioned may each be substituted by one or more R.sup.3 radicals.

4. The electronic device as claimed in claim 1, wherein Z.sup.1 is the same or different at each instance and is selected from C and CR.sup.1.

5. The electronic device as claimed in claim 1, wherein k is 0.

6. The electronic device as claimed in claim 1, wherein R.sup.1 is the same or different at each instance and is selected from H, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the aromatic ring systems and the heteroaromatic ring systems are each substituted by R.sup.4 radicals; and R.sup.2 is the same or different at each instance and is selected from H, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the aromatic ring systems and the heteroaromatic ring systems are each substituted by R.sup.4 radicals; and R.sup.3 is the same or different at each instance and is selected from H, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the aromatic ring systems and the heteroaromatic ring systems are each substituted by R.sup.4 radicals; and R.sup.4 is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups, the aromatic ring systems and the heteroaromatic ring systems are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl or alkoxy groups may be replaced by —C≡C—, R.sup.5C═CR.sup.5—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —NR.sup.5—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.5—; and R.sup.5 is H.

7. The electronic device as claimed in claim 1, wherein the compound containing a structural unit of formula (I) conforms to one of the following formulae: ##STR00662## ##STR00663## ##STR00664## ##STR00665## where Ar.sup.2 is selected from aromatic ring systems which have 4 to 40 aromatic ring atoms and are substituted by R.sup.A radicals and heteroaromatic ring systems which have 3 to 40 aromatic ring atoms and are substituted by R.sup.A radicals, where R.sup.A is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.A radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, 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; and where Z.sup.1 is the same or different at each instance and is CR.sup.1 or N.

8. The electronic device as claimed in claim 7, wherein Ar.sup.2 is fused-on benzene substituted by one or more R.sup.A radicals.

9. The electronic device as claimed in claim 7, wherein R.sup.A is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the alkyl and alkoxy groups, the aromatic ring systems and the heteroaromatic ring systems are each substituted by R.sup.4 radicals.

10. The electronic device as claimed in claim 9, wherein it is an organic electroluminescent device and comprises anode, cathode and at least one emitting layer, and in that the compound containing a structural element of the formula (I) is present in an emitting layer together with at least one phosphorescent emitter, or in that the compound containing a structural element of the formula (I) is present in a layer selected from hole blocker layers, electron transport layers and electron injection layers.

11. The organic electroluminescent device as claimed in claim 10, wherein the compound containing a structural element of the formula (I) is present in an emitting layer of the device together with at least one phosphorescent emitter and at least one further compound, where the further compound is a matrix material.

12. The organic electroluminescent device as claimed in claim 11, wherein the further compound is selected from hole-transporting matrix materials, preferably carbazole compounds, biscarbazole compounds, indolocarbazole compounds and indenocarbazole compounds.

13. A compound of one of the formulae ##STR00666## ##STR00667## ##STR00668## ##STR00669## where Ar.sup.2 is selected from aromatic ring systems which have 4 to 40 aromatic ring atoms and are substituted by R.sup.A radicals and heteroaromatic ring systems which have 3 to 40 aromatic ring atoms and are substituted by R.sup.A radicals, where R.sup.A is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.A radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, 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; and where Z.sup.1 is the same or different at each instance and is CR.sup.1 or N; Ar.sup.1 is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by one or more R.sup.3 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by one or more R.sup.3 radicals; R.sup.1 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, 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; R.sup.2 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, 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; R.sup.3 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, 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; R.sup.4 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, 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; R.sup.5 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN; where there is at least one R.sup.1, R.sup.2, R.sup.3 or R.sup.A group selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals (radical A), heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals (radical B), N(R.sup.4).sub.2 (radical C).

14. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 13, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.1, R.sup.2 or R.sup.3 in formula (I).

15. A formulation comprising at least one compound as claimed in claim 13, and at least one solvent.

16. A method comprising incorporating the compound as claimed in claim 13 in an electronic device.

17. A process for preparing a compound as claimed in claim 13, wherein either a) proceeding from a compound of the formula (Int-I) or (Int-II) ##STR00670## where HetAr is a heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is substituted by R.sup.2 radicals, and Z.sup.1 is the same or different at each instance and is selected from CR.sup.1 or N, in a first step a halogen substituent is introduced, preferably Cl, Br or I, in a second step an aromatic or heteroaromatic ring system is introduced on the nitrogen atom of the lactam group in an Ullmann coupling reaction, and in a third step an amino group bearing the aromatic or heteroaromatic ring systems as substituents is introduced in the position of the halogen substituent via a Buchwald coupling, or an aromatic or heteroaromatic ring system is introduced via a Suzuki coupling; or b) proceeding from a compound of a formula (Int-III) ##STR00671## where Z.sup.1 is the same or different at each instance and is CR.sup.1 or N; and HetAr is a heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is substituted by R.sup.2 radicals; and Ar.sup.1 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by one or more R.sup.3 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by one or more R.sup.3 radicals; wherein in a first step halogen substituents, preferably Br, are introduced in the two positions vicinal to the nitrogen atom of HetAr, and in a second step the amide groups of the formula (Int-III) bind to the positions of the halogen substituents on HetAr in a metal-catalyzed coupling reaction, so as to form two lactam rings; or c) a starting compound of a formula (Int-IV) ##STR00672## where Ar is an aromatic ring system which has 6 to 40 aromatic ring atoms and is substituted by R.sup.2 radicals, and where Z.sup.1 is the same or different at each instance and is selected from CR.sup.1 or N, in a first step is converted at its ketone group to the corresponding hydroxylamine derivative, this hydroxylamine derivative is then converted further in a second step in a Beckmann rearrangement, and the resultant lactam derivative is then converted in a third step at the nitrogen of the lactam unit in an Ullmann coupling.

18. A mixture comprising at least one compound as claimed in claim 13 and at least one further compound selected from matrix materials for phosphorescent emitters.

Description

EXAMPLES

A) Synthesis Examples

Example a: 7-Bromo-6H-indolo[1,2-a]quinazolin-5-one

[0171] ##STR00310##

[0172] 5.5 g (23.5 mmol) of 6H-indolo[1,2-a]quinazolin-5-one are initially charged in 150 ml of CH.sub.2Cl.sub.2. Subsequently, a solution of 4 g (22.5 mmol) of NBS in 100 ml of acetonitrile is added dropwise in the dark at 0° C., the mixture is allowed to come to room temperature and stirring is continued at this temperature for 4 h. Subsequently, 150 ml of water are added to the mixture and extraction is effected with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4 and the solvents are removed under reduced pressure. The product is subjected to extractive stirring with hot hexane and filtered off with suction. Yield: 5.5 g (17.6 mmol), 75% of theory, purity by .sup.1H NMR about 98%.

[0173] The following compounds are obtained in an analogous manner:

TABLE-US-00003 Ex. Reactant Product Yield  1a [00311] [00312] 69%  2a [00313] [00314] 58%  2a [00315] [00316] 52%  4a [00317] [00318] 63%  5a [00319] [00320] 66%  6a [00321] [00322] 69%  7a [00323] [00324] 57%  8a [00325] [00326] 71%  9a [00327] [00328] 70% 11a [00329] [00330] 88% 12a [00331] [00332] 89% 13a [00333] [00334] 78% 14a [00335] [00336] 71% 15a [00337] [00338] 57% 16a [00339] [00340] 69% 17a [00341] [00342] 73% 18a [00343] [00344] 57%

Example b: 7-Bromo-6-(3,5-diphenylphenyl)indolo[1,2-a]quinazolin-5-one

[0174] ##STR00345##

[0175] 31 g (100 mmol) of 7-bromo-6H-indolo[1,2-a]quinazolin-5-one, 106 g (300 mmol) of 5′-iodo-[1,1′;3′,1″]terphenyl, 2.3 g (20 mmol) of L-proline and 5.2 g (27 mmol, 0.11 eq) of copper(I) iodide are stirred in 100 ml 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 by rotary evaporation. The residue is purified by chromatography (EtOAc/hexane: 2/3). The yield is 30 g (57 mmol), 57% of theory.

[0176] The following compounds are obtained in an analogous manner:

TABLE-US-00004 Ex. Reactant 1 Reactant 2 Product Yield  1b [00346] [00347] [00348] 58%  2b [00349] [00350] [00351] 54%  3b [00352] [00353] [00354] 58%  4b [00355] [00356] [00357] 57%  5b [00358] [00359] [00360] 59%  6b [00361] [00362] [00363] 61%  7b [00364] [00365] [00366] 64%  8b [00367] [00368] [00369] 79%  9b [00370] [00371] [00372] 64% 10b [00373] [00374] [00375] 68% 11b [00376] [00377] [00378] 64% 12b [00379] [00380] [00381] 72% 13b [00382] [00383] [00384] 76% 14b [00385] [00386] [00387] 71% 15b [00388] [00389] [00390] 61%

Example c: 6-(3,5-Diphenylphenyl)-7-phenylindolo[1,2-a]quinazolin-5-one

[0177] ##STR00391##

[0178] 13.3 g (110.0 mmol) of phenylboronic acid, 59 g (110.0 mmol) of 7-bromo-6-(3,5-diphenylphenyl)indolo[1,2-a]quinazolin-5-one and 44.6 g (210.0 mmol) of tripotassium phosphate are suspended in 500 ml of toluene, 500 ml of dioxane and 500 ml of water. To this suspension are added 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/iso-propanol and finally sublimed under high vacuum. The purity is 99.9%. The yield is 77 g (88 mmol), corresponding to 80% of theory.

[0179] The following compounds are obtained in an analogous manner:

TABLE-US-00005 Ex. Reactant 1 Reactant 2 Product Yield 1c [00392] [00393] [00394] 75% 2c [00395] [00396] [00397] 70% 3c [00398] [00399] [00400] 79% 4c [00401] [00402] [00403] 69% 5c [00404] [00405] [00406] 63% 6c [00407] [00408] [00409] 82% 7c [00410] [00411] [00412] 75% 8c [00413] [00414] [00415] 88% 9c [00416] [00417] [00418] 84% 10c [00419] [00420] [00421] 63% 11c [00422] [00423] [00424] 77% 12c [00425] [00426] [00427] 74% 13c [00428] [00429] [00430] 89% 14c [00431] [00432] [00433] 75% 15c [00434] [00435] [00436] 59% 16c [00437] [00438] [00439] 67% 17c [00440] [00441] [00442] 66% 18c [00443] [00444] [00445] 62% 19c [00446] [00447] [00448] 71% 20c [00449] [00450] [00451] 70% 21c [00452] [00453] [00454] 73% 22c [00455] [00456] [00457] 84% 23c [00458] [00459] [00460] 69% 24c [00461] [00462] [00463] 77% 25c [00464] [00465] [00466] 81% 26c [00467] [00468] [00469] 86% 27c [00470] [00471] [00472] 80% 28c [00473] [00474] [00475] 76% 29c [00476] [00477] [00478] 71% 30c [00479] [00480] [00481] 65%

Example d: Indolo[1,2-a]benzimidazol-11-one Oxime

[0180] ##STR00482##

[0181] To an initial charge of 33 g (147 mmol) of indolo[1,2-a]benzimidazol-11-one in 300 ml of pyridine/200 of methanol is then added 20.5 g of hydroxylammonium chloride in portions. This is followed by heating at 60° C. for 3.5 hours. After the reaction has ended, the precipitated solids are filtered off with suction and washed with water and 1M HCl, and then with methanol. The yield is 32.4 g (138 mmol), corresponding to 92% of theory. The following compounds can be prepared in an analogous manner:

TABLE-US-00006 Ex. Reactant 1 Product Yield 1d [00483] [00484] 89% 2d [00485] [00486] 91% 3d [00487] [00488] 90% 4d [00489] [00490] 93%

Example e: Lactam Synthesis

A) 5H-Benzimidazolo[1,2-a]quinoxalin-6-one

B) 6H-Benzimidazolo[1,2-a]quinazolin-5-one

[0182] ##STR00491##

[0183] An initial charge of 33 g (140 mmol) of indolo[1,2-a]benzimidazol-11-one oxime in 300 ml of polyphosphoric acid is finally heated to 170° C. for 12 hours. After the reaction has ended, the mixture is added to ice, extracted with ethyl acetate, separated and concentrated. The precipitated solids are filtered off with suction and washed with ethanol. The isomers are separated by chromatography.

[0184] Yield: 30 g (127 mmol) of the A+B mixture, 94% of theory, purity: 98.0% by HPLC. Recrystallization from ethyl acetate/toluene (1:3) affords 14 g (42%) of (A) and 16 g (48%) of (B).

[0185] The following compounds are prepared in an analogous manner:

TABLE-US-00007 Yield Ex. Reactant 1 Product (A) Product (B) (A)/(B) 1e [00492] [00493] [00494] 44%/45% 2e [00495] [00496] [00497] 40%/43% 3e [00498] [00499] [00500] 42%/40% 4e [00501] [00502] [00503] 38%/41%

Example 5-(3-Phenylphenyl)benzimidazolo[1,2-a]quinoxalin-6-one

[0186] ##STR00504##

[0187] An initial charge of 13.5 g (25 mmol, 1.00 eq.) of 5H-benzimidazolo[1,2-a]quinoxalin-6-one, 21.3 ml (128 mmol, 5.2 eq.) of 3-bromobiphenyl and 7.20 g of potassium carbonate (52.1 mmol, 2.10 eq.) in 220 ml of dry DMF is inertized under argon. Subsequently, 0.62 g (2.7 mmol, 0.11 eq) of 1,3-di(2-pyridyl)propane-1,3-dione and 0.52 g (2.7 mmol, 0.11 eq) of copper(I) iodide are added and the mixture is heated at 140° C. for three days. After the reaction has ended, the mixture is concentrated cautiously on a rotary evaporator, and the precipitated solids are filtered off with suction and washed with water and ethanol. The crude product is purified twice by means of a hot extractor (toluene/heptane 1:1), and the solids obtained are recrystallized from toluene. After sublimation, 8.2 g (12 mmol, 48%) of the desired target compound is obtained.

[0188] The following compounds can be prepared in an analogous manner:

TABLE-US-00008 Ex. Reactant 1 Reactant 1 Product Yield 2f [00505] [00506] [00507] 68% 3f [00508] [00509] [00510] 71% 4f [00511] [00512] [00513] 63% 5f [00514] [00515] [00516] 77% 6f [00517] [00518] [00519] 65% 7f [00520] [00521] [00522] 64% 8f [00523] [00524] [00525] 64% 9f [00526] [00527] [00528] 67% 10f [00529] [00530] [00531] 71% 11f [00532] [00533] [00534] 52% 12f [00535] [00536] [00537] 50% 13f [00538] [00539] [00540] 52% 14f [00541] [00542] [00543] 61% 15f [00544] [00545] [00546] 69% 16f [00547] [00548] [00549] 54%

Example g) 5-Phenyl-3-(9-phenylcarbazol-3-yl)benzimidazolo[1,2-a]quinoxalin-6-one

[0189] ##STR00550##

[0190] 27.3 (70 mmol) of 3-bromo-5-phenylbenzimidazolo[1,2-a]quinoxalin-6-one, 20.8 g (75 mmol) of phenylcarbazole-3-boronic acid and 14.7 g (139 mmol) of sodium carbonate are suspended in 200 ml of toluene, 52 ml of ethanol and 100 ml of water. 80 mg (0.69 mmol) of tetrakisphenylphosphinepalladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The residue is recrystallized from heptane/dichloromethane. The yield is 29 g (54 mmol), corresponding to 77% of theory.

[0191] The following compound is obtained in an analogous manner:

TABLE-US-00009 Ex. Reactant 1 Reactant 2 Product Yield 2g [00551] [00552] [00553] 71% 3g [00554] [00555] [00556] 82% 4g [00557] [00558] [00559] 76% 5g [00560] [00561] [00562] 77% 6g [00563] [00564] [00565] 54% 7g [00566] [00567] [00568] 77% 8g [00569] [00570] [00571] 70% 9g [00572] [00573] [00574] 62% 10g [00575] [00576] [00577] 62% 11g [00578] [00579] [00580] 60% 12g [00581] [00582] [00583] 74% 13g [00584] [00585] [00586] 70% 14g [00587] [00588] [00589] 68% 15g [00590] [00591] [00592] 71% 16g [00593] [00594] [00595] 64% 17g [00596] [00597] [00598] 86% 18g [00599] [00600] [00601] 80% 19g [00602] [00603] [00604] 84% 20g [00605] [00606] [00607] 76% 21g [00608] [00609] [00610] 81% 22g [00611] [00612] [00613] 80% 23g [00614] [00615] [00616] 83% 24g [00617] [00618] [00619] 80% 25g [00620] [00621] [00622] 79% 26g [00623] [00624] [00625] 77% 27g [00626] [00627] [00628] 81% 28g [00629] [00630] [00631] 80% 29g [00632] [00633] [00634] 76% 30g [00635] [00636] [00637] 69%

Example h: 2-(2,5-Dibromopyrrol-1-yl)-N1,N3-diphenylbenzene-1,3-dicarboxamide

[0192] ##STR00638##

[0193] 4.5 g (12 mmol) of N1,N3-diphenyl-2-pyrrol-1-ylbenzene-1,3-dicarboxamide are initially charged in 150 ml of CH.sub.2Cl.sub.2. Subsequently, a solution of 4 g (22.5 mmol) of NBS in 100 ml of acetonitrile is added dropwise in the dark at −5° C., the mixture is allowed to come to room temperature and stirring is continued at this temperature for 4 h. Subsequently, 150 ml of water are added to the mixture and extraction is effected with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4 and the solvents are removed under reduced pressure. The product is subjected to extractive stirring with hot hexane and filtered off with suction. Yield: 3.9 g (17.6 mmol), 70% of theory, purity by .sup.1H NMR about 98%.

Example i: Cyclization

[0194] ##STR00639##

[0195] 11.8 g (25 mmol) of 2-(2,5-dibromopyrrol-1-yl)-N1,N3-diphenylbenzene-1,3-dicarboxamide are dissolved in 600 ml of toluene and degassed with argon for 30 minutes. Subsequently, 8.1 g (84.8 mmol) of sodium t-butoxide, 476 mg (2.12 mmol) of palladium(II) acetate and 4.2 ml (4.24 mmol) of tri-t-butylphosphine (1.0M in toluene) are added and the mixture is stirred under reflux overnight. After the reaction has ended, 200 ml of water are added to the mixture, and the organic phase is removed and extracted twice with water. The organic phase is dried over sodium sulfate and concentrated to about 80 ml on a rotary evaporator. The precipitated solids are filtered off with suction and purified by means of hot extraction in toluene. The product is recrystallized three times with toluene/heptane and then sublimed. 6.6 g (17.0 mmol, 71%) of the desired target compound having HPLC purity >99.9% are obtained.

B) Device Examples

[0196] The examples which follow present the use of the materials of the invention in OLEDs.

[0197] Glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating, first with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plates form the substrates to which the OLEDs are applied.

[0198] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/hole blocker layer (HBL)/electron transport layer (ETL)/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 tables 1a to 1c. The data of the OLEDs are listed in tables 2a to 2c. The materials required for production of the OLEDs are shown in table 3.

[0199] 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 coevaporation. What is meant here by data in such a form as A:B:C (45%:45%:10%) is that material A is present in the layer in a proportion by volume of 45%, material B in a proportion by volume of 45%, and material C in a proportion by volume of 10%. In an analogous manner, the electron transport layer or one of the other layers may also consist of a mixture of two materials.

[0200] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra and the external quantum efficiency (EQE, measured in %) as a function of the luminance, calculated from current-voltage-luminance characteristics assuming Lambertian emission characteristics, are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. EQE1000 denotes the external quantum efficiency which is attained at 1000 cd/cm.sup.2.

[0201] The materials of the invention are used in examples E1 to E6 as matrix material in the emission layer of green-phosphorescing OLEDs.

TABLE-US-00010 TABLE 1a Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness E1 HATCN SpMA1 SpMA2 IC1:21c:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (59%:29%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E2 HATCN SpMA1 SpMA2 25g:IC2:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (44%:44%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E3 HATCN SpMA1 SpMA2 16g:IC2:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (29%:59%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E4 HATCN SpMA1 SpMA2 IC1:19g:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (54%:29%:17%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E5 HATCN SpMA1 SpMA2 29g:IC3:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (29%:59%:12%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E6 HATCN SpMA1 SpMA2 IC3:30g:TEG1 ST2 ST2:LiQ LiQ 5 nm 215 nm 20 nm (54%:29%:17%) 30 nm 10 nm (50%:50%) 30 nm 1 nm

[0202] All compounds of the invention give very good results for external quantum efficiency.

TABLE-US-00011 TABLE 2a Data of the OLEDs U1000 EQE 1000 CIE x/y at Ex. (V) (%) 1000 cd/m.sup.2 E1 3.3 18 0.36/0.61 E2 3.5 18.5 0.35/0.61 E3 3.6 16 0.34/0.62 E4 3.9 19 0.35/0.61 E5 3.1 20 0.35/0.64 E6 3.2 19.5 0.36/0.61

[0203] Further materials of the invention are used in examples E7 to E9 as matrix material in the emission layer of red-phosphorescing OLEDs.

TABLE-US-00012 TABLE 1b Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness E7 HATCN SpMA1 SpMA2 11b:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm E8 HATCN SpMA1 SpMA2 15b:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm E9 HATCN SpMA1 SpMA2 28g:TER5 ST2 ST2:LiQ LiQ 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm 1 nm

[0204] Both compounds of the invention give very good results for external quantum efficiency.

TABLE-US-00013 TABLE 2b Data of the OLEDs U1000 CIE x/y at EQE 1000 Ex. (V) 1000 cd/m.sup.2 % E7 3.5 0.67/0.34 17.1 E8 3.1 0.67/0.33 19.6 E9 3.2 0.67/0.34 18.9

[0205] A further material of the invention is used in examples E10 and E11 respectively as ETL and HBL of blue-fluorescing OLEDs. Use as ETL and HBL in phosphorescent OLEDs is likewise possible.

TABLE-US-00014 TABLE 1c Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness E10 HATCN SpMA1 SpMA2 M2:SEB — 25g:LiQ LiQ 5 nm 195 nm 10 nm (95%:5%) 20 nm (50%:50%) 30 nm 1 nm E11 HATCN SpMA1 SpMA2 M2:SEB 25g ST2 LiQ 5 nm 195 nm 10 nm (95%:5%) 20 nm 10 nm 20 nm 3 nm

[0206] The compound of the invention gives very good results for external quantum efficiency, at operating voltages U1000 in the range of 4-5 V.

TABLE-US-00015 TABLE 2c Data of the OLEDs EQE 1000 CIE x/y at Ex. (%) 1000 cd/m.sup.2 E10 7 0.14/0.15 E11 8 0.14/0.15

TABLE-US-00016 TABLE 3 Structural formulae of the materials for the OLEDs [00640] [00641] [00642] [00643] [00644] [00645] [00646] [00647] [00648] [00649] [00650] [00651] [00652] [00653] [00654] [00655] [00656] [00657] [00658] [00659] [00660]