MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to electron-deficient heteroaromatic compounds which are substituted by dibenzofuran or dibenzothiophene derivatives and by carbazoles or amines, in particular for use as triplet matrix materials in organic electroluminescent devices. The invention furthermore relates to a process for the preparation of the compounds according to the invention and to electronic devices comprising these compounds.

Claims

1.-15. (canceled)

16. A compound of the formula (1), ##STR00491## where: A is on each occurrence, identically or differently, CR.sup.1 or N, where a maximum of two groups A per ring stand for N; Y.sup.1 is O or S; L is on each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R HetAr is a group of the formula (2) or (3), ##STR00492## where the dashed bonds represent the linking of this group to the dibenzofuran or dibenzothiophene derivative and to L; X is on each occurrence, identically or differently, CR.sup.2 or N, with the proviso that at least one symbol X stands for N; N.sup.1 is a group of the following formula (4), (5) or (6), ##STR00493## where the dashed bond represents the linking of this group to L; Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring, atoms, which may be substituted by one or more radicals R.sup.3; W is on each occurrence, identically or differently, CR.sup.1 or N, where a maximum of two groups W stand for N, or two adjacent groups W together stand for a group of the following, formula (7) or (8), where the group of the formula (4) or (6) contains a maximum of one group of the formula (7) or (8), and the remaining groups W stand, identically or differently on each occurrence, for CR.sup.1 or N, ##STR00494## where the dashed bonds indicate the linking of this group, and A has the meanings given above; Y.sup.2, Y.sup.3 are, identically or differently on each occurrence, O, NR.sup.4, S, C(R.sup.4).sub.2, Si(R.sup.4).sub.2, BR.sup.4 or C═O, where the radical R.sup.4 which is bonded to N is not equal to H; R.sup.1, R.sup.2, R.sup.3, R.sup.4 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.2).sub.2, N(R.sup.5).sub.2, C(═O)Ar.sup.2, C(═O)R.sup.5, P(═O)(Ar.sup.2).sub.2, P(Ar.sup.2).sub.2, B(Ar.sup.2).sub.2, Si(Ar.sup.2).sub.3, Si(R.sup.5).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl group having 2 to 20 C atoms, each of which may be substituted by one or more radicals R.sup.5, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.5C═CR.sup.5, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, P(═O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.5, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.5; two adjacent substituents R.sup.1 or two adjacent substituents R.sup.3 or two adjacent substituents R.sup.4 here may optionally faun an aliphatic, aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R.sup.5; Ar.sup.2 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R.sup.5; two radicals Ar.sup.2 which are bonded to the same N atom, P atom or B atom here may also be bridged to one another by a single bond or a bridge selected from N(R.sup.5), C(R.sup.5).sub.2, O or S; R.sup.5 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; two or more adjacent substituents R.sup.5 here may form an aliphatic ring system with one another; with the proviso that Y.sup.1 stands for O if the group N.sup.1 stands for a group of the formula (4) which does not contain a group of the formula (7) or (8).

17. The compound according to claim 16 of the formula (1 a), ##STR00495## where symbols used have the meanings given in claim 16, n stands for 0, 1, 2 or 3 and m stands for 0, 1, 2, 3 or 4.

18. The compound according to claim 16 of one of the formulae (1b) to (1i), ##STR00496## ##STR00497## where the symbols used have the meanings given in claim 16.

19. The compound according to claim 16, wherein the groups of the formula (2) and (3) are selected from the groups of the formulae (2-1) to (2-7) and (3-1), ##STR00498## where the dashed bond and * represents the linking of these groups to the dibenzofuran or dibenzothiophene derivative in formula (1), the dashed bond and # represents the linking of these groups to L or, for L equal to a single bond, to N.sup.1, and R.sup.2 has the meanings given in claim 16.

20. The compound according to claim 16, wherein the groups of the formulae (2) and (3) are selected from the groups of the formulae (2-1a) to (3-1a), ##STR00499## where the dashed bond and * represents the linking of these groups to the dibenzofuran or dibenzothiophene derivative in formula (1), the dashed bond and # represents the linking of these groups to L or, for L equal to a single bond, to N.sup.1, and R.sup.2 stands for FT or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.sup.5.

21. The compound according to claim 16, wherein the groups of the formulae (4) and (6) are selected from the groups of the formulae (4-1), (4-2) and (6-1), ##STR00500## where R.sup.1 and m have the meanings given in claim 16, and furthermore: two adjacent groups W together stand for a group of the formula (7a) or (8a) and the other two groups W stand for CR.sup.1, ##STR00501## where Y.sup.2, Y.sup.3, R.sup.1 and m have the meanings given in claim 16.

22. The compound according to claim 21, wherein the group of the formula (4-1) is selected from the groups of the formulae (4-1a) to (4-if) and in that the group of the formula (4-2) is selected from the groups of the formulae (4-2a) to (4-2f), ##STR00502## ##STR00503## where the symbols and indices used have the meanings given in claim 16.

23. The compound according to claim 16, wherein Ar.sup.1 in the group of the formula (5) stands, identically or differently on each occurrence, for an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each ease be substituted by one or more radicals R.sup.3.

24. The compound according to claim 16, wherein R.sup.1 is selected from the group consisting of H, D, F, CN, N(Ar.sup.2).sub.2, C(═O)Ar.sup.2, P(═O)(Ar.sup.2).sub.2, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or an alkenyl group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R.sup.5, where one or more non-adjacent CH.sub.2 groups may be replaced by O and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5, or an aralkyl or heteroaralkyl group having 5 to 25 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; two substituents R.sup.1 which are bonded to adjacent carbon atoms here may optionally form a monocyclic or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R.sup.5.

25. The compound according to claim 16 for which: Y.sup.1 is O or S; L is on each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; HetAr is a group of one of the formulae (2-1) to (2-7) or (3-1) according to claim 19; N.sup.1 is a group of the formula (4-1), (4-2), (5) or (6-1), ##STR00504## two adjacent groups W together stand for a group of the formula (7a) or (8a) and the other two groups W stand for CR.sup.1, ##STR00505## Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3; Y.sup.2, Y.sup.3 are, identically or differently on each occurrence, O, S, NR.sup.4 or C(R.sup.4).sub.2, where the radical R.sup.4 which is bonded to N is not equal to H; R.sup.1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, N(Ar.sup.2).sub.2, C(═O)Ar.sup.2, P(═O)(Ar.sup.2).sub.2, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or an alkenyl group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R.sup.5, where one or more non-adjacent CH.sub.2 groups may be replaced by O and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5, or an aralkyl or heteroaralkyl group having 5 to 25 aromatic ring atoms, which may be substituted by one or more radicals. R.sup.1; two substituents R.sup.1 which are bonded to adjacent carbon atoms here may optionally form a monocyclic or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R.sup.5; R.sup.2 is on each occurrence, identically or differently, H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5; R.sup.3 is on each occurrence, identically or differently, H, an alkyl group having 1 to 4 C atoms or an aromatic or heteroaromatic ring system having 5 to 14 aromatic ring atoms; R.sup.4 is, for Y.sup.2 or Y.sup.3═NR.sup.4, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5; and is, for Y.sup.2 or Y.sup.3═C(R.sup.4).sub.2, on each occurrence, identically or differently, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an alkenyl group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R.sup.5, where one or more non-adjacent CH.sub.2 groups may be replaced by O and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5; the two substituents R.sup.4 here may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.sup.5; R.sup.5 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; the other symbols and indices have the meanings given in claim 16.

26. A process for the preparation of a compound according to claim 16, starting from an optionally substituted 1-halodibenzofuran or 1-halodibenzothiophene, comprising the following steps: a) optionally conversion of the halogen group into a boronic acid or a boronic acid derivative; b) introduction of the group HetAr by a coupling reaction; c) introduction of the group N.sup.1 or the group -L-N.sup.1 by a coupling reaction.

27. A formulation comprising at least one compound according to claim 16 and at least one further compound and/or a solvent.

28. A method comprising utilizing the compound according to claim 16 or the formulation according to claim 27 in an electronic device.

29. An electronic device comprising at least one compound according to claim 16 or the formulation according to claim 27, wherein the electronic devise 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-sensitised solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

30. The electronic device according to claim 29, wherein the device is an organic electroluminescent device and wherein the compound according to claim 16 is employed as matrix material for fluorescent or phosphorescent emitters in an emitting layer and/or in an electron-transport layer and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport layer.

Description

EXAMPLES

[0123] The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The corresponding CAS numbers are also indicated in each case from the compounds known from the literature.

a) 6-Bromo-2-fluoro-2′-methoxybiphenyl

[0124] ##STR00098##

[0125] 200 g (664 mmol) of 1-bromo-3-fluoro-2-iodobenzene, 101 g (664 mmol) of 2-methoxyphenylboronic acid and 137.5 g (997 mmol) of sodium tetraborate are dissolved in 1000 ml of THF and 600 ml of water and degassed. 9.3 g (13.3 mmol) of bis(triphenylphosphine)palladium(II) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is subsequently stirred at 70° C. under a protective-gas atmosphere for 48 h. The cooled solution is replenished with toluene, washed a number of times with water, dried and evaporated. The product is purified by column chromatography on silica gel with toluene/heptane (1:2). Yield: 155 g (553 mmol), 83% of theory.

[0126] The following compounds are prepared analogously:

TABLE-US-00001 Starting Starting material 1 material 2 Product Yield a1 [00099] [00100] [00101] 77% a2 [00102] [00103] [00104] 74% a3 [00105] [00106] [00107] 76% a4 [00108] [00109] [00110] 71%

b) 6′-Bromo-2′-fluorobiphenyl-2-ol

[0127] ##STR00111##

[0128] 112 g (418 mmol) of 6-bromo-2-fluoro-2′-methoxybiphenyl are dissolved in 2 l of dichloromethane and cooled to 5° C. 41.01 ml (431 mmol) of boron tribromide are added dropwise to this solution over the course of 90 min., and stirring is continued overnight. Water is subsequently slowly added to the mixture, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4, evaporated in a rotary evaporator and purified by chromatography. Yield: 104 g (397 mmol), 98% of theory.

[0129] The following compounds are prepared analogously:

TABLE-US-00002 Starting material 1 Product Yield b1 [00112] [00113] 92% b2 [00114] [00115] 90% b3 [00116] [00117] 93% b4 [00118] [00119] 94%

c) 1-Bromodibenzofuran

[0130] ##STR00120##

[0131] 111 g (416 mmol) of 6′-bromo-2′-fluorobiphenyl-2-ol are dissolved in 2 l of SeccoSolv® DMF (max. 0.003% of H.sub.2O) and cooled to 5° C. 20 g (449 mmol) of sodium hydride (60% suspension in paraffin oil) are added in portions to this solution, and the mixture is stirred for a further 20 min. after the addition is complete and then heated at 100° C. for 45 min. After cooling, 500 ml of ethanol are subsequently slowly added to the mixture, which is then evaporated to dryness in a rotary evaporator and then purified by chromatography. Yield: 90 g (367 mmol), 88.5% of theory.

[0132] The following compounds are prepared analogously:

TABLE-US-00003 Starting material 1 Product Yield c1 [00121] [00122] 81% c2 [00123] [00124] 78% c3 [00125] [00126] 73% c4 [00127] [00128] 79%

d) Dibenzofuran-1-boronic acid

[0133] ##STR00129##

[0134] 180 g (728 mmol) of 1-bromodibenzofuran are dissolved in 1500 ml of dry THF and cooled to −78° C. 305 ml (764 mmol/2.5 M in hexane) of n-butyl-lithium are added over the course of about 5 min. at this temperature, and stirring is subsequently continued at −78° C. for 2.5 h. 151 g (1456 mmol) of trimethyl borate are then added as rapidly as possible at this temperature, and the reaction mixture is allowed to come slowly to room temperature (about 18 h). The reaction solution is washed with water, and the precipitated solid and the organic phase are dried azeotropically with toluene. The crude product is washed by stirring with toluene/methylene chloride at about 40° C. and filtered off with suction. Yield: 146 g (690 mmol), 95% of theory.

[0135] The following compounds are prepared analogously:

TABLE-US-00004 Starting material 1 Product Yield d1 [00130] [00131] 81% d2 [00132] [00133] 78% d3 [00134] [00135] 73% d4 [00136] [00137] 79% d5 [00138] [00139] 73%

e) 2-Chloro-4-dibenzofuran-1-yl-6-phenyl-1,3,5-triazine

[0136] ##STR00140##

[0137] 37.8 g (153.0 mmol) of dibenzofuran-1-boronic acid, 34.6 g (153.0 mmol) of 2,4-dichloro-6-phenyl-1,3,5-triazine and 17 g (168.0 mmol) of sodium carbonate are suspended in 120 ml of toluene, 300 ml of dioxane and 300 ml of water. 1.7 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene and from dichloromethane/heptane. The yield is 46 g (131 mmol), corresponding to 86% of theory.

[0138] The following compounds are prepared analogously:

TABLE-US-00005 Starting material Starting material 1 2 Product Yield e1 [00141] [00142] [00143] 74% e2 [00144] [00145] [00146] 79% e3 [00147] [00148] [00149] 78% e4 [00150] [00151] [00152] 79% e5 [00153] [00154] [00155] 68% e6 [00156] [00157] [00158] 80% e7 [00159] [00160] [00161] 85% e8 [00162] [00163] [00164] 84% e9 [00165] [00166] [00167] 80% e10 [00168] [00169] [00170] 83% e11 [00171] [00172] [00173] 80%

f) 10-(4-Dibenzofuran-1-yl-6-phenyl-1,3,5-triazin-2-yl)-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b ]fluorene

[0139] ##STR00174##

[0140] 8 g (28.2 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene are dissolved in 225 ml of dimethylformamide under a protective-gas atmosphere, and 1.5 g of NaH, 60% in mineral oil (37.5 mmol), are added. After 1 h at room temperature, a solution of 11.3 g (31.75 mmol) of 2-chloro-4-dibenzofuran-1-yl-6-phenyl-1,3,5-triazine in 75 ml of dimethylformamide is added dropwise. The reaction mixture is stirred at room temperature for 12 h, then poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is extracted with hot toluene and recrystallised from chlorobenzene (HPLC purity >99.9%) and sublimed in vacuo. The yield is 15.2 g (25 mmol), corresponding to 80% of theory.

[0141] The following compounds are prepared analogously:

TABLE-US-00006 +0 Starting material 1 Starting material 2 Product Yield f1 [00175] [00176] [00177] 69% f2 [00178] [00179] [00180] 73% f3 [00181] [00182] [00183] 79% f4 [00184] [00185] [00186] 78% f5 [00187] [00188] [00189] 75% f6 [00190] [00191] [00192] 68% f7 [00193] [00194] [00195] 80% f8 [00196] [00197] [00198] 88% f9 [00199] [00200] [00201] 74% f10 [00202] [00203] [00204] 80% f11 [00205] [00206] [00207] 80% f12 [00208] [00209] [00210] 78% f13 [00211] [00212] [00213] 83% f14 [00214] [00215] [00216] 85% f15 [00217] [00218] [00219] 75% f16 [00220] [00221] [00222] 83% f17 [00223] [00224] [00225] 85% f18 [00226] [00227] [00228] 79% f19 [00229] [00230] [00231] 76% f20 [00232] [00233] [00234] 75% f21 [00235] [00236] [00237] 65% f22 [00238] [00239] [00240] 80% f23 [00241] [00242] [00243] 84% f24 [00244] [00245] [00246] 78% f25 [00247] [00248] [00249] 81% f26 [00250] [00251] [00252] 83% f27 [00253] [00254] [00255] 78% f28 [00256] [00257] [00258] 85% f29 [00259] [00260] [00261] 85% f30 [00262] [00263] [00264] 75% f31 [00265] [00266] [00267] 82% f32 [00268] [00269] [00270] 85% f33 [00271] [00272] [00273] 75% f34 [00274] [00275] [00276] 78% f35 [00277] [00278] [00279] 79% f36 [00280] [00281] [00282] 62% f37 [00283] [00284] [00285] 76% f38 [00286] [00287] [00288] 83% f39 [00289] [00290] [00291] 78% f40 [00292] [00293] [00294] 81% f41 [00295] [00296] [00297] 82% f42 [00298] [00299] [00300] 78% f43 [00301] [00302] [00303] 82% f44 [00304] [00305] [00306] 87% f45 [00307] [00308] [00309] 73% f46 [00310] [00311] [00312] 75% f47 [00313] [00314] [00315] 77% f48 [00316] [00317] [00318] 79% f49 [00319] [00320] [00321] 82% f50 [00322] [00323] [00324] 82%

g) 10-[3-(4-Dibenzofuran-1-yl-6-phenyl-1,3,5-triazin-2-yl)phenyl]-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

[0142] ##STR00325##

[0143] 56 g (140 mmol) of B43-[7,7-dimethylindeno[2,1-b]carbazol-5[7H]-yl)-phenyl]boronic acid, 49 g (140 mmol) of 2-chloro-4-dibenzofuran-1-yl-6-phenyl-1,3,5-triazine and 78.9 ml (158 mmol) of Na.sub.2CO.sub.3 (2 M solution in water) are suspended in 120 ml of toluene, 120 ml of ethanol and 100 ml of water. 2.6 g (2.2 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and evaporated to dryness. The residue is recrystallised from toluene. The residue is extracted with hot toluene, recrystallised from chlorobenzene (HPLC purity >99.9%) and sublimed in vacuo. The yield is 82 g (120 mmol), corresponding to 87% of theory.

[0144] The following compounds are prepared analogously:

TABLE-US-00007 Starting material 1 Starting material 2 Product Yield g1 [00326] [00327] [00328] 86% g2 [00329] [00330] [00331] 82% g3 [00332] [00333] [00334] 80% g4 [00335] [00336] [00337] 79% g5 [00338] [00339] [00340] 80% g6 [00341] [00342] [00343] 89% g7 [00344] [00345] [00346] 85% g8 [00347] [00348] [00349] 80%

h) Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine

[0145] ##STR00350##

[0146] 24.0 g (142 mmol, 1.2 eq.) of 4-aminobiphenyl (CAS 92-67-1) and 32.0 g (117 mmol, 1.0 eq.) of 2-bromo-9,9′-dimethylfluorene (CAS 28320-31-2) are initially introduced in 950 ml of toluene and saturated with argon for 30 minutes. 1.0 g (1.8 mmol, 0.02 eq.) of 1,1′-bis(diphenylphosphino)ferrocene (CAS 12150-46-8), 350 mg (1.6 mmol, 0.01 eq.) of palladium(II) acetate (GAS 3375-31-3) and 29 g (300 mmol, 2.6 eq.) of sodium tortbutoxide (CAS 865-48-5) are subsequently added, and the mixture is heated under reflux overnight. When the reaction is complete, the batch is diluted with 300 ml of toluene and extracted with water. The organic phase is dried over sodium sulfate, and the solvent is removed in a rotary evaporator. 50 ml of ethyl acetate are added to the brown oil, and the mixture is added to a mixture of heptane/ethyl acetate 20:1. The solid formed is filtered off with suction and washed with heptane. Drying gives 29 g (80 mmol, 69%) of the product having an HPLC purity of 99.1%.

[0147] The following compounds can be obtained analogously:

TABLE-US-00008 Starting Starting material 1 material 2 Product Yield h1 [00351] [00352] [00353] 71% h2 [00354] [00355] [00356] 61% h3 [00357] [00358] [00359] 78% h4 [00360] [00361] [00362] 82% h5 [00363] [00364] [00365] 62% h6 [00366] [00367] [00368] 47% h7 [00369] [00370] [00371] 92% h8 [00372] [00373] [00374] 75% h9 [00375] [00376] [00377] 84% h10 [00378] [00379] [00380] 62%

j) Bisbiphenyl-4-yl-(4-dibenzofuran-1-yl-6-phenyl-1,3,5-triazin-2-yl)-amine

[0148] ##STR00381##

[0149] A degassed solution of 49 g (140 mmol) of 2-chloro-4-dibenzofuran-1-yl-6-phenyl-1,3,5-triazine and 43 g (140 mmol) of bisbiphenyl-4-ylamine in 600 ml of toluene is saturated with N.sub.2 for 1 h. Then, firstly 2.09 ml (8.6 mmol) of P(tBu).sub.3, then 1.38 g (6.1 mmol) of palladium(II) acetate are added to the solution, and 17.7 g (185 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 ml of water are carefully added. The aqueous phase is washed with 3×50 ml of toluene, dried over MgSO.sub.4, and the solvent is removed in vacuo. The crude product is then purified by chromatography on silica gel with heptane/ethyl acetate (20:1). The residue is recrystallised from toluene and finally sublimed in a high vacuum (p=5×10.sup.−6 mbar). The yield is 60 g (94 mmol), corresponding to 69% of theory.

[0150] The following compounds can be obtained analogously:

TABLE-US-00009 Starting Starting material 1 material 2 Product Yield j1 [00382] [00383] [00384] 67% j2 [00385] [00386] [00387] 64% j3 [00388] [00389] [00390] 61% j4 [00391] [00392] [00393] 60% j5 [00394] [00395] [00396] 64% j6 [00397] [00398] [00399] 58% j7 [00400] [00401] [00402] 63% j8 [00403] [00404] [00405] 67% j9 [00406] [00407] [00408] 67% j10 [00409] [00410] [00411] 65%
The following compounds can be obtained analogously to procedure (g):

TABLE-US-00010 j11 [00412] [00413] [00414] 72% j12 [00415] [00416] [00417] 76% j13 [00418] [00419] [00420] 69% j14 [00421] [00422] [00423] 75% j15 [00424] [00425] [00426] 77% j16 [00427] [00428] [00429] 79%

k) 10-[3-(4-Dibenzofuran-1-yl-6-phenyl-1,3,5-triazin-2-yl)phenyl]-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

[0151] ##STR00430##

[0152] 15.5 g (43.3 mmol) of 2-chloro-4-dibenzofuran-1-yl-6-phenyl-1,3,5-triazine and 19.3 g (48 mmol) of 3-(12,12-dimethyl-12H-10-azaindeno[2,1-b]-fluoren-10-yl)boronic acid are dissolved in 80 ml of toluene and degassed. 281 ml of a degassed 2M K.sub.2CO.sub.3 solution in water and 2.5 g (2.2 mmol) of Pd(OAc).sub.2 are added. The reaction mixture is subsequently stirred at 80° C. under a protective-gas atmosphere for 48 h. The cooled solution is replenished with toluene, washed a number of times with water, dried and evaporated. The product is purified by column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed in a high vacuum (p=5×10.sup.−7 mbar). The purity is 99.9%. Yield: 25.4 g (37 mmol), 78% of theory.

[0153] The following compounds can be obtained analogously:

TABLE-US-00011 Starting Starting material 1 material 2 Product Yield k1 [00431] [00432] [00433] 71% k2 [00434] [00435] [00436] 78% k3 [00437] [00438] [00439] 75% k4 [00440] [00441] [00442] 82% k5 [00443] [00444] [00445] 63% k6 [00446] [00447] [00448] 87% k7 [00449] [00450] [00451] 69% k8 [00452] [00453] [00454] 85%

[0154] Production of OLEDs

[0155] The data for various OLEDs are presented in the following Examples V1 to E21 (see Tables 1 and 2).

[0156] Pre-treatment for Examples V1-E21: Glass plates coated with structured

[0157] ITO (indium tin oxide) in a thickness of 50 nm are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP Al 4083 from Heraeus Precious Metals GmbH, Germany, applied by spin coating from aqueous solution) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied.

[0158] The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL) electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium cathode with a thickness of 100 nm. The precise structure of the OLEDs is shown in Table 1. The materials required for the production of the OLEDs are shown in Table 3.

[0159] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or materials in a certain proportion by volume by co-evaporation. An expression such as IC1:IC3:TEG1 (55%:35%:10%) here means that material IC1 is present in the layer in a proportion by volume of 55%, IC3 is present in the layer in a proportion of 35% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

[0160] The OLEDs are characterised by standard methods. 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 per cent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines), assuming Lambert emission characteristics, and the lifetime are determined. The electroluminescence spectra are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The expression U1000 in Table 2 denotes the voltage required for a luminous density of 1000 cd/m.sup.2. CE1000 and PEb 1000 denote the current and power efficiencies achieved at 1000 cd/m.sup.2. Finally, EQE1000 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminous density drops to a certain proportion L1 from the initial luminous density on operation at constant current. An expression of L0;j0=4000 cd/m.sup.2 and L1=70% in Table 2 means that the lifetime indicated in column LT corresponds to the time after which the initial luminous density drops from 4000 cd/m.sup.2 to 2800 cd/m.sup.2. Analogously, L0;j0=20 mA/cm.sup.2, L1=80% means that the luminous density on operation at 20 mA/cm.sup.2 drops to 80% of its initial value after time LT.

[0161] The data of the various OLEDs are summarised in Table 2. Examples V1-V4 are OLEDs comparative examples in accordance with the prior art, Examples E1-E21 show data of OLEDs according to the invention.

[0162] Some of the examples are explained in greater detail below in order to illustrate the advantages of the compounds according to the invention.

[0163] Use of Mixtures According to the Invention in the Emission Layer of Phosphorescent OLEDs

[0164] On use as matrix materials in phosphorescent OLEDs, the materials according to the invention give rise to significant improvements over the prior art with respect to the lifetime of the components. Use of compounds EG1 to EG5 according to the invention in combination with the green-emitting dopant TEG1 enables an increase in the lifetime by about 20% to 40% over the prior art to be observed (comparison of Examples V1 with E1, E2 and V2 with E3 as well as V3 with E4 and V4 with E5).

TABLE-US-00012 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. Thickness Thickness Thickness Thickness Thickness Thickness Thickness V1 SpA1 HATCN SpMA1 SdT1:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm V2 SpA1 HATCN SpMA1 SdT2:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm V3 SpA1 HATCN SpMA1 SdT3:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm V4 SpA1 HATCN SpMA1 SdT4:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E1 SpA1 HATCN SpMA1 EG1:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E2 SpA1 HATCN SpMA1 EG2:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E3 SpA1 HATCN SpMA1 EG3:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E4 SpA1 HATCN SpMA1 EG4:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E5 SpA1 HATCN SpMA1 EG5:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E6 SpA1 HATCN SpMA1 EG6:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E7 SpA1 HATCN SpMA1 EG7:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (95%:5%) 30 nm 10 nm 30 nm E8 SpA1 HATCN SpMA1 EG8:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E9 SpA1 HATCN SpMA1 EG9:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E10 SpA1 HATCN SpMA1 IC1:TEG1 — ST2:EG10(50%:50%) LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm E11 SpA1 HATCN SpMA1 EG11:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E12 SpA1 HATCN SpMA1 IC1:TEG1 EG12 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E13 SpA1 HATCN SpMA1 EG13:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E14 SpA1 HATCN SpMA1 EG14:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E15 SpA1 HATCN SpMA1 EG15:TEG1 ST2 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E16 SpA1 HATCN SpMA1 EG16:IC4:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm E17 SpA1 HATCN SpMA1 EG17:IC4:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm E18 SpA1 HATCN SpMA1 EG18:IC4:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm E19 SpA1 HATCN SpMA1 EG19:IC4:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm E20 SpA1 HATCN SpMA1 EG20:TER3 — ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (92%:8%) 30 nm 40 nm E21 SpA1 HATCN SpMA1 EG21:TER3 — ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (92%:8%) 30 nm 40 nm

TABLE-US-00013 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at LT Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 L.sub.o; j.sub.o L1 % (h) V1 3.2 60 59 16.3% 0.33/0.63 20 mA/cm.sup.2 80 130 V2 3.5 59 53 16.2% 0.32/0.64 20 mA/cm.sup.2 80 135 V3 3.6 63 55 16.9% 0.31/0.65 20 mA/cm.sup.2 80 145 V4 3.3 54 51 15.2% 0.33/0.62 20 mA/cm.sup.2 80 120 E1 3.3 60 57 16.0% 0.34/0.63 20 mA/cm.sup.2 80 175 E2 3.2 60 59 16.1% 0.32/0.63 20 mA/cm.sup.2 80 160 E3 3.4 61 56 16.4% 0.35/0.62 20 mA/cm.sup.2 80 170 E4 3.5 61 55 16.8% 0.31/0.64 20 mA/cm.sup.2 80 175 E5 3.3 53 50 14.9% 0.32/0.63 20 mA/cm.sup.2 80 150 E6 3.2 63 62 16.9% 0.32/0.64 20 mA/cm.sup.2 80 170 E7 3.4 54 50 14.6% 0.32/0.64 20 mA/cm.sup.2 80 120 E8 3.5 60 54 16.5% 0.32/0.64 20 mA/cm.sup.2 80 155 E9 3.5 53 48 14.4% 0.31/0.64 20 mA/cm.sup.2 80 140 E10 3.1 67 68 18.1% 0.33/0.63 20 mA/cm.sup.2 80 145 E11 3.2 62 61 16.8% 0.33/0.63 20 mA/cm.sup.2 80 165 E12 3.3 67 64 17.9% 0.33/0.63 20 mA/cm.sup.2 80 140 E13 3.4 53 49 14.9% 0.32/0.63 20 mA/cm.sup.2 80 130 E14 3.3 57 54 15.8% 0.34/0.62 20 mA/cm.sup.2 80 190 E15 3.4 52 48 14.7% 0.32/0.63 20 mA/cm.sup.2 80 155 E16 3.5 62 56 16.8% 0.32/0.63 20 mA/cm.sup.2 80 85 E17 3.6 62 54 16.7% 0.33/0.63 20 mA/cm.sup.2 80 100 E18 3.5 61 55 16.5% 0.34/0.63 20 mA/cm.sup.2 80 120 E19 3.7 62 53 16.9% 0.31/0.64 20 mA/cm.sup.2 80 110 E20 4.4 13 9 11.9% 0.67/0.33 4000 cd/m.sup.2 80 340 E21 4.6 13 9 12.3% 0.67/0.33 4000 cd/m.sup.2 80 290

TABLE-US-00014 TABLE 3 Structural formulae of the materials for the OLEDs [00455] [00456] [00457] [00458] [00459] [00460] [00461] [00462] [00463] [00464] [00465] [00466] [00467] [00468] [00469] [00470] [00471] [00472] [00473] [00474] [00475] [00476] [00477] [00478] [00479] [00480] [00481] [00482] [00483] [00484] [00485] [00486] [00487] [00488] [00489] [00490]