MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to mixtures comprising at least one phosphorescent dopant and at least one compound of one of the formulae (1) and (2), and the use thereof in electronic devices, especially in organic electroluminescent devices.

Claims

1.-13. (canceled)

14. A mixture comprising at least one phosphorescent dopant and at least one compound of one of the formulae (1) and (2): ##STR00457## where the symbols and indices used are as follows: X is the same or different at each instance and is N or CR.sup.3, where not more than 2 X per heteroaryl group are N; L is the same or different at each instance and is an (m+n)-valent aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.4 radicals; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)Ar, P(O)(Ar).sub.2, S(O)Ar, S(O).sub.2Ar, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sup.2, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms and is optionally substituted in each case by one or more R.sup.4 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by CC, Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, CO, CS, CSe, P(O)(R.sup.4), SO, SO.sub.2, O, S or CONR.sup.4 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.4 radicals, or a combination of these systems; at the same time, two or more R.sup.1 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)Ar, P(O)(Ar).sub.2, S(O)Ar, S(O).sub.2Ar, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, N(Ar).sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 60 carbon atoms and is optionally substituted in each case by one or more R.sup.4 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by CC, Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, CO, CS, CSe, P(O)(R.sup.4), SO, SO.sub.2, O, S or CONR.sup.4 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.4 radicals, or a combination of these systems; at the same time, two or more R.sup.2 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.3 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)Ar, P(O)(Ar).sub.2, S(O)Ar, S(O).sub.2Ar, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, N(R.sup.4).sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms and is optionally substituted in each case by one or more R.sup.4 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by CC, Si(R.sup.1).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, CO, CS, CSe, P(O)(R.sup.4), SO, SO.sub.2, O, S or CONR.sup.4 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.4 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.3 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 60 aromatic ring atoms and may also be substituted in each case by one or more R.sup.4 radicals, R.sup.4 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)R.sup.5, P(O)(R.sup.5).sub.2, S(O)R.sup.5, S(O).sub.2R.sup.5, CN, NO.sub.2, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, N(R.sup.5).sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.5 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, P(O)(R.sup.5), SO, SO.sub.2, O, S or CONR.sup.5 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which is optionally substituted by one or more R.sup.5 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.5 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.4 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.5 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.6).sub.2, C(O)R.sup.6, P(O)(R.sup.6).sub.2, S(O)R.sup.6, S(O).sub.2R.sup.6, CR.sup.6C(R.sup.6).sub.2, CN, NO.sub.2, Si(R.sup.6).sub.3, B(OR.sup.6).sub.2, OSO.sub.2R.sup.6, N(R.sup.6).sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.6 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by R.sup.6CCR.sup.6, Si(R.sup.6).sub.2, CO, CNR.sup.6, P(O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which is optionally substituted by one or more R.sup.6 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.6 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.6 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.5 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.6 is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aryl or heteroaryl group which has 5 to 60 ring atoms and is optionally substituted by one or more R.sup.7 radicals, or a combination of these groups; R.sup.7 is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms; and m, n are the same or different at each instance and are 0, 1, 3, 4, 5, 6 or 7; where m+n is equal to or superior to 2.

15. The mixture according to claim 14, wherein the at least one compound of one of the formulae (1) and (2) is at least one compound of one of the foiniulae (3) and (4): ##STR00458## where the symbols and indices have the definitions given in claim 14.

16. The mixture according to claim 14, wherein the at least one phosphorescent dopant comprises a compound which, at room temperature, exhibits luminescence from an excited state with spin multiplicity >1.

17. The mixture according to claim 16, wherein the at least one phosphorescent dopant comprises a compound which emits light under suitable excitation and contains at least one atom of atomic number greater than 20.

18. The mixture according to claim 17, wherein the at least one phosphorescent dopant comprises a compound containing at least one atom of atomic number greater than 56 and less than 80.

19. The mixture according to claim 18, wherein the at least one phosphorescent dopant comprises a compound containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold and/or europium.

20. The mixture according to claim 19, wherein the at least one phosphorescent dopant comprises a compound selected from the formulae (D-1) to (D-4) ##STR00459## where R.sup.4 has the same definition as described above for formula (1), and the further symbols used are as follows: DCy is the same or different at each instance and is a cyclic group which contains at least one donor atom or bears it as a substituent via which the cyclic group is bonded to the metal, and which may in turn bear one or more R.sup.4 substituents; the DCy and CCy groups are joined to one another via a covalent bond; CCy is the same or different at each instance and is a cyclic group which contains a carbon atom via which the cyclic group is bonded to the metal, and which may in turn bear one or more R.sup.4 substituents; A is the same or different at each instance and is a monoanionic ligand with bidentate chelation, and B is the same or different at each instance and is a compound comprising at least one donor atom which binds to the metal.

21. A process for producing a the mixture according to claim 14, wherein the compound of the formula (1) or formula (2) is formed by one or more coupling reactions and/or cyclizations.

22. A formulation comprising at least one mixture according to claim 14 and one or more solvents.

23. A solution, a suspension or a miniemulsion comprising at least one mixture according to claim 14 and one or more solvents.

24. An electronic device comprising the mixture according to claim 14.

25. A matrix material for a phosphorescent compound which comprises a compound according to either of the formulae (1) and (2) ##STR00460## where the symbols and indices used are as follows: X is the same or different at each instance and is N or CR.sup.3, where not more than 2 X per heteroaryl group are N; L is the same or different at each instance and is an (m+n)-valent aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.4 radicals; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)Ar, P(O)(Ar).sub.2, S(O)Ar, S(O).sub.2Ar, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sup.2, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms and is optionally substituted in each case by one or more R.sup.4 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by CC, Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, CO, CS, CSe, P(O)(R.sup.4), SO, SO.sub.2, O, S or CONR.sup.4 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.4 radicals, or a combination of these systems; at the same time, two or more R.sup.1 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)Ar, P(O)(Ar).sub.2, S(O)Ar, S(O).sub.2Ar, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, N(Ar).sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 60 carbon atoms and is optionally substituted in each case by one or more R.sup.4 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, CO, CS, CSe, P(O)(R.sup.4), SO, SO.sub.2, O, S or CONR.sup.4 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.4 radicals, or a combination of these systems; at the same time, two or more R.sup.2 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.3 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)Ar, P(O)(Ar).sub.2, S(O)Ar, S(O).sub.2Ar, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, N(R.sup.4).sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms and is optionally substituted in each case by one or more R.sup.4 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, CO, CS, CSe, P(O)(R.sup.4), SO, SO.sub.2, O, S or CONR.sup.4 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.4 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.3 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 60 aromatic ring atoms and may also be substituted in each case by one or more R.sup.4 radicals, R.sup.4 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)R.sup.5, P(O)(R.sup.5).sub.2, S(O)R.sup.5, S(O).sub.2R.sup.5, CN, NO.sub.2, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, N(R.sup.5).sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.5 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, P(O)(R.sup.5), SO, SO.sub.2, O, S or CONR.sup.5 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which is optionally substituted by one or more R.sup.5 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.5 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.4 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.5 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.6).sub.2, C(O)R.sup.6, P(O)(R.sup.6).sub.2, S(O)R.sup.6, S(O).sub.2R.sup.6, CR.sup.6C(R.sup.6).sub.2, CN, NO.sub.2, Si(R.sup.6).sub.3, B(OR.sup.6).sub.2, OSO.sub.2R.sup.6, N(R.sup.6).sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.6 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by R.sup.6CCR.sup.6, Si(R.sup.6).sub.2, CO, CNR.sup.6, P(O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which is optionally substituted by one or more R.sup.6 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.6 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.6 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.5 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.6 is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aryl or heteroaryl group which has 5 to 60 ring atoms and is optionally substituted by one or more R.sup.7 radicals, or a combination of these groups; R.sup.7 is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms; and m, n are the same or different at each instance and are 0, 1, 2, 3, 4, 5, 6 or 7; where m+n is equal to or superior to 2.

26. The electronic device as claimed in claim 24, wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic dye-sensitized solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

27. The electronic device according to claim 24, wherein the device is an organic electroluminescent device and the mixture is used in an emitting layer.

Description

WORKING EXAMPLES

[0161] ##STR00228##

[0162] Scheme 1 shows a synthesis of the base skeleton in analogy to Monatshefte fuer Chemie, 141(8), 877-881; 2010.

[0163] A second option for the synthesis is shown by Schemes 2a, 2b and 2c:

##STR00229##

[0164] In this scheme, R is any radical and X is a leaving group, for example a halide or tosylate.

[0165] First of all, a 4H-3,1-benzoxazine-2,4(1H)-dione is reacted with an amine and an aldehyde under acid catalysis. The corresponding 2,3-dihydro-1H-quinazolin-4-one is obtained. The latter can be oxidized with potassium permanganate to the quinazolinone base skeleton. Because of the mild reaction conditions, it is possible to use substituted aromatics. In this way, it is possible in a simple manner to introduce groups which allow further coupling reactions.

##STR00230##

[0166] The leaving groups introduced can be converted, for example, by organometallic coupling reactions. Scheme 2b cites, as an example, a Buchwald coupling or a Suzuki coupling.

[0167] By multiple coupling reactions, it is possible to form the compounds of the formula (2).

##STR00231##

[0168] The formation of compounds of the formula (2) is also possible by the method shown in Scheme 2c. This involves, in analogy to Scheme 2a, reacting a 4H-3,1-benzoxazine-2,4(1H)-dione derivative with an amine and an aldehyde under acid catalysis, where the amine and/or the aldehyde has at least one further amino and/or aldehyde group. Preference is given to amino or aldehyde groups bonded to aromatic or heteroaromatic ring systems. In this way, two or more 4H-3,1-benzoxazine-2,4(1H)-dione derivatives are joined to one another. The compound obtained can be oxidized with potassium permanganate to the compound of formula (2).

Example 1: 2-(4-Bromophenyl)-3-phenyl-2,3-dihydro-1H-quinazolin-4-one

[0169] ##STR00232##

[0170] 11 ml (121 mmol) of phenylamine and 18 g (110 mmol) of 4H-3,1-benzoxazine-2,4(1H)-dione are refluxed in 500 ml of acetic acid. After 45 min, 22.4 g (121 mmol) of 4-bromobenzaldehyde dissolved in acetic acid are added and stirring of the mixture is continued under reflux overnight. After cooling, the solution is diluted with water/ice and filtered with suction. The residue is subjected to extraction by stirring with heptane and ethanol. The yield is 36 g (95 mmol), 86% of theory.

[0171] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00004 Ex. Reactant 1 Reactant 2 Reactant 3 Product [%] 1a [00233] [00234] [00235] [00236] 82 1b [00237] [00238] [00239] [00240] 86 1c [00241] [00242] [00243] [00244] 74 1d [00245] [00246] [00247] [00248] 70 1e [00249] [00250] [00251] [00252] 80 1f [00253] [00254] [00255] [00256] 68 1g [00257] [00258] [00259] [00260] 79 1h [00261] [00262] [00263] [00264] 84 1j [00265] [00266] [00267] [00268] 78 1i [00269] [00270] [00271] [00272] 81 1k [00273] [00274] [00275] [00276] 76 1l [00277] [00278] [00279] [00280] 76 1m [00281] [00282] [00283] [00284] 65 1n [00285] [00286] [00287] [00288] 70 1o [00289] [00290] [00291] [00292] 87

[0172] In analogy, the following compounds can be obtained when bifunctional groups are used:

TABLE-US-00005 Yield Ex. Reactant 1 Reactant 2 Reactant 3 Product [%] 1p [00293] [00294] [00295] [00296] 67 1q [00297] [00298] [00299] [00300] 61 1r [00301] [00302] [00303] [00304] 59 1s [00305] [00306] [00307] [00308] 48 1t [00309] [00310] [00311] [00312] 56

Example 2: 2-(4-Bromophenyl)-3-phenyl-3H-quinazolin-4-one

[0173] ##STR00313##

[0174] 36 g (95 mmol) of 2-(4-bromophenyl)-3-phenyl-2,3-dihydro-1H-quinazolin-4-one are dissolved in 300 ml of DMF. 15 g (95 mmol) of potassium permanganate are added in portions to this solution, and the mixture is stirred at room temperature for 3 hours. After this time, the rest of the potassium permanganate is filtered off, and the solution is concentrated and purified by chromatography (eluent: heptane/dichloromethane, 5:1). The residue is recrystallized from toluene and from dichloromethane/isopropanol and finally sublimed under high vacuum; purity is 99.9%. The yield is 22 g (58 mmol), 61% of theory.

[0175] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00006 Yield Ex. Reactant 3 Product [%] 2a [00314] [00315] 82 2b [00316] [00317] 86 2c [00318] [00319] 74 2d [00320] [00321] 70 2e [00322] [00323] 80 2f [00324] [00325] 68 2g [00326] [00327] 79 2h [00328] [00329] 84 2j [00330] [00331] 78 2l [00332] [00333] 81 2k [00334] [00335] 76 2l [00336] [00337] 82 2m [00338] [00339] 79 2n [00340] [00341] 81 2o [00342] [00343] 83

[0176] In analogy, the following compounds can be obtained when 2 eq. of KMnO.sub.4 are used:

TABLE-US-00007 Yield Ex. Reactant 1 Product [%] 2p [00344] [00345] 67 2q [00346] [00347] 61 2r [00348] [00349] 59 2s [00350] [00351] 48 2t [00352] [00353] 56

Example 3: 2-(4-Dibenzofuran-4-ylphenyl)-3-phenyl-3H-quinazolin-4-one

[0177] ##STR00354##

[0178] 41.3 g (110.0 mmol) of 4-dibenzofuranboronic acid, 41 g (110.0 mmol) of 2-(4-bromophenyl)-3-phenyl-3H-quinazolin-4-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. Added to this suspension are 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/isopropanol and finally sublimed under high vacuum; purity is 99.9%. The yield is 41 g (90 mmol), corresponding to 82% of theory.

[0179] In an analogous manner, the following compounds are obtained;

TABLE-US-00008 Yield Ex Reactant 1 Reactant 2 Product [%] 3a [00355] [00356] [00357] 83 3b [00358] [00359] [00360] 82 3c [00361] [00362] [00363] 81 3d [00364] [00365] [00366] 83 3e [00367] [00368] [00369] 88 3f [00370] [00371] [00372] 68 3g [00373] [00374] [00375] 75 3h [00376] [00377] [00378] 76 3j [00379] [00380] [00381] 83 3i [00382] [00383] [00384] 85 3k [00385] [00386] [00387] 88 3l [00388] [00389] [00390] 86 3m [00391] [00392] [00393] 76 3n [00394] [00395] [00396] 86 3o [00397] [00398] [00399] 67 3p [00400] [00401] [00402] 82

[0180] In analogy, the following compounds are obtained with 0.5 eq. of boron compound:

TABLE-US-00009 Yield Ex. Reactant 1 Reactant 2 Product [%] 3q [00403] [00404] [00405] 86 3r [00406] [00407] [00408] 81 3s [00409] [00410] [00411] 83

Example 4: 2-[4-(3,6-Diphenylcarbazol-9-yl)-phenyl]-3-phenyl-3H-quinazolin-4-one

[0181] ##STR00412##

[0182] 32 g (102.4 mmol) of 3,6-diphenyl-9H-carbazole, 42 g (112 mmol) of 2-(4-bromophenyl)-3-phenyl-3H-quinazolin-4-one and 2.3 g (10.2 mmol) of 1,3-di[2-pyridyl]propane-1,3-dione, 28.3 g (204 mmol) of potassium carbonate and 1.9 g (10.2 mmol) of copper iodide in 1000 ml of DMF are stirred under reflux for 90 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 and purified by chromatography (EtOAc/hexane: 2/3). The residue is recrystallized from toluene and from dichloromethane and finally sublimed under high vacuum; purity is 99.9%. The yield is 47 g (77 mmol), corresponding to 69% of theory.

[0183] In an analogous manner, the following compounds are obtained:

TABLE-US-00010 Yield Ex. Reactant 1 Reactant 2 Product [%] 4a [00413] [00414] [00415] 65 4b [00416] [00417] [00418] 66 4c [00419] [00420] [00421] 74 4d [00422] [00423] [00424] 71 4e [00425] [00426] [00427] 70 4f [00428] [00429] [00430] 65 4g [00431] [00432] [00433] 69 4h [00434] [00435] [00436] 72

Example 5: Production of the OLEDs

[0184] In examples 11 to 115 which follow (see Tables 1 and 2), the data of various OLEDs are presented. Cleaned glass plaques (cleaning in laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 20 min, for improved processing, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulphonate), purchased as CLEVIOS P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180 C. for 10 min. These coated glass plaques form the substrates to which the OLEDs are applied.

[0185] The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/interlayer (IL)/electron blocker layer (EBL) emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 1. A reference such as 4a in the table relates to the materials shown in the tables for the examples. The further materials required for production of the OLEDs are shown in table 3.

[0186] All materials are applied by thermal vapour 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 4a:BIC1:TEG1 (30%:60%:10%) mean here that the material 4a is present in the layer in a proportion by volume of 30%, BIC1 in a proportion of 60% and TEG1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0187] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter 01000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

[0188] The data for the various OLEDs are collated in Table 2.

TABLE-US-00011 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness thickness I1 SpA1 HATCN SpMA1 2q:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (85%:15%) (50%:50%) 30 nm 30 nm I2 SpA1 HATCN SpMA1 2r:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (85%:15%) (50%:50%) 30 nm 30 nm I3 SpA1 HATCN SpMA1 2s:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (85%:15%) (50%:50%) 30 nm 30 nm I4 SpA1 HATCN SpMA1 2s:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 30 nm I5 SpA1 HATCN SpMA1 2s:IC1:TEG1 ST1 ST1:LiQ 70 nm 5 nm 90 nm (42%:42%:16%) 10 nm (50%:50%) 30 nm 30 nm I6 SpA1 HATCN SpMA1 2f:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:15%) (50%:50%) 30 nm 30 nm I7 SpA1 HATCN SpMA1 4:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:15%) (50%:50%) 30 nm 30 nm I8 SpA1 HATCN SpMA1 3d:TER1 ST1:LiQ 90 nm 5 nm 130 nm (92%:8%) (50%:50%) 40 nm 40 nm I9 SpA1 HATCN SpMA1 3m:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:15%) (50%:50%) 30 nm 30 nm I10 SpA1 HATCN SpMA1 4a:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 30 nm I11 SpA1 HATCN SpMA1 4a:IC1:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (45%:45%:10%) (50%:50%) 30 nm 30 nm I12 SpA1 HATCN SpMA1 4a:BIC1:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) (50%:50%) 30 nm 30 nm I13 SpA1 HATCN SpMA1 4h:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 30 nm I14 SpA1 HATCN SpMA1 4h:BIC1:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (60%:30%:10%) (50%:50%) 30 nm 30 nm I15 SpA1 HATCN SpMA1 4h:TEG2 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:15%) (50%:50%) 30 nm 30 nm

TABLE-US-00012 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 E1 3.8 57 48 15.8% 0.32/0.63 E2 3.7 56 47 15.7% 0.33/0.62 E3 3.7 59 50 16.5% 0.32/0.62 E4 3.9 61 50 16.6% 0.32/0.63 E5 3.2 63 62 17.1% 0.33/0.63 E6 3.6 62 56 17.8% 0.32/0.62 E7 3.7 60 50 16.8% 0.32/0.63 E8 4.9 10.3 6.6 11.0% 0.67/0.33 E9 3.4 61 57 17.4% 0.34/0.62 E10 3.6 49 43 13.7% 0.34/0.62 E11 3.1 52 54 14.7% 0.33/0.62 E12 3.6 47 41 13.1% 0.32/0.63 E13 3.9 58 48 16.3% 0.32/0.63 E14 3.9 54 43 15.1% 0.33/0.62 E15 3.8 57 47 16.1% 0.34/0.61

TABLE-US-00013 TABLE 3 Structural formulae of the materials for the OLEDs [00437] HATCN [00438] SpA1 [00439] LiQ [00440] ST1 [00441] TEG1 [00442] TEG2 [00443] IC1 [00444] SpMA1 [00445] TER1 [00446] BIC1 [00447] IC1 [00448] 2q [00449] 2r [00450] 2s [00451] 2f [00452] 3d [00453] 3m [00454] 4 [00455] 4a [00456] 4h