MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present application relates to a compound of a formula (I) which contains a spirobifluorene basic structure condensed onto a benzofuran unit. The application furthermore relates to a process for the preparation of the compound of the formula (I), and to the use of the compound of the formula (I) in an electronic device.

Claims

1.-18. (canceled)

19. A compound of the formula (I-5) ##STR00597## which is optionally substituted by a radical R.sup.1 at one or more positions on the basic structure of the formula (I-5) and the group of the formula (B) which are depicted as unsubstituted; and which has the following definitions of the variables: A is on each occurrence, identically or differently, a group of the formula (A1) which is bonded via the bond marked by #; ##STR00598## Ar.sup.1 is on each occurrence, identically or differently, a single bond; Ar.sup.2 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; R.sup.0 is on each occurrence, identically or differently, H, D, F, CN, Si(R.sup.3).sub.3, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2; R.sup.1, R.sup.2 are on each occurrence, identically or differently, H, D, F, C(═O)R.sup.3, CN, Si(R.sup.3).sub.3, N(Ar.sup.3).sub.2, N(R.sup.3).sub.2, P(═O)(R.sup.3).sub.2, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sub.3, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3; two or more radicals R.sup.1 or R.sup.2 is optionally linked to one another and may form a ring; Ar.sup.3 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3; R.sup.3 is on each occurrence, identically or differently, H, D, F, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(Ar.sup.3).sub.2, 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, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.4 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally 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, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4; two or more radicals R.sup.3 is optionally linked to one another and may form a ring; and R.sup.4 is on each occurrence, identically or differently, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D, F or CN; two or more substituents R.sup.4 is optionally linked to one another and may form a ring.

20. The compound according to claim 19, wherein R.sup.0 is on each occurrence, identically or differently, H, D, F, 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, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3.

21. A compound of one of the formulae (II-5) ##STR00599## which is optionally substituted at one or more free positions by a radical R.sup.1, wherein R.sup.1 are on each occurrence, identically or differently, H, D, F, C(═O)R.sup.3, CN, Si(R.sup.3).sub.3, N(Ar.sup.3).sub.2, N(R.sup.3).sub.2, P(═O)(R.sup.3).sub.2, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sub.3, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3; two or more radicals R.sup.1 or R.sup.2 is optionally linked to one another and may form a ring; Ar.sup.3 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3; R.sup.0 is on each occurrence, identically or differently, H, D, F, CN, Si(R.sup.3).sub.3, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2; R.sup.3 is on each occurrence, identically or differently, H, D, F, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(Ar.sup.3).sub.2, 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, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.4 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally 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, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4; two or more radicals R.sup.3 is optionally linked to one another and may form a ring; R.sup.4 is on each occurrence, identically or differently, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D, F or CN; two or more substituents R.sup.4 is optionally linked to one another and may form a ring; Z is selected on each occurrence, identically or differently, from F, Cl, Br, I, B(OR.sup.3).sub.2, OSO.sub.2R.sub.3, S(═O)R.sup.3 and S(═O).sub.2R.sup.3; and t is on each occurrence, identically or differently, 0 or 1, where at least one index t per formula is equal to 1.

22. A process for the preparation of the compound according to claim 19, which comprises preparing firstly the spirobifluorene basic structure, and, in a later step, an arylamino or carbazole group or an aryl or heteroaryl group which is substituted by an arylamino or carbazole group is introduced via an organometallic coupling reaction.

23. An oligomer, polymer or dendrimer containing one or more compounds according to claim 19, where the bond(s) to the polymer, oligomer or dendrimers is optionally localised at any positions in formula (I-5) that are substituted by R.sup.0, R.sup.1 or R.sup.2.

24. A formulation comprising at least one compound according to claim 19 and at least one solvent.

25. An electronic device comprising at least one compound according to claim 19.

26. The electronic device according to claim 25, wherein the device is selected from the group consisting of organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, organic light-emitting electrochemical cells, organic laser diodes and organic electroluminescent devices.

27. An organic electroluminescent device wherein the compound according to claim 19 is present in an emitting layer.

28. The compound according to claim 19, wherein Ar.sup.2 is phenyl, which may be substituted by one or more radicals R.sup.2.

29. The compound according to claim 19, wherein R.sup.0 is H or D

30. The compound according to claim 19, wherein R.sup.1 is on each occurrence, identically or differently, H, D, OR.sup.3 or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3; two or more radicals R.sup.1 are optionally linked to one another and may form a ring.

31. The compound according to claim 19, wherein R.sup.2 is on each occurrence, identically or differently, H, D, a straight-chain alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms.

32. The compound according to claim 19, wherein R.sup.3 is on each occurrence, identically or differently, H, D, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4.

Description

WORKING EXAMPLES

A) Synthesis Examples

A-1) Example 1: Synthesis of Compounds (1-1) to (1-13)

[0136] ##STR00248##

Synthesis of 4-(2-bromophenyl)dibenzofuran Int-1

[0137] 100 g (462 mmol) of dibenzofuran-4-boronic acid, 106 g (439 mmol) of 1,2-dibromobenzene and 10.7 g (9.2 mmol) of Pd(Ph.sub.3P).sub.4 are suspended in 980 ml of dioxane. 979 ml of 2 M potassium carbonate solution are slowly 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 purified by chromatography on silica gel. Yield: 87 g (270 mmol), 58% of theory, purity according to HPLC>98%.

Synthesis of Intermediate Int-7

[0138] 31 g (90 mmol) of 4-(2-bromophenyl)dibenzofuran are initially introduced in 300 ml of THF at −78° C. 40 ml of BuLi (2 M in hexane) are added dropwise at this temperature. After 1 hour, 16.9 g (94 mmol) of fluoren-9-one in 200 ml of THF are added dropwise. The batch is left to stir overnight at room temperature, added to ice-water and extracted with dichloromethane. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed in vacuo, and the residue is, without further purification, heated under reflux at 100° C. overnight with 94 ml of HCl and 1074 ml of AcOH. After cooling, the precipitated solid is filtered off with suction, washed once with 100 ml of water, three times with 100 ml of ethanol each time and subsequently recrystallised from heptane. Yield: 23.1 g (57 mmol), 58%; purity approx. 98% according to .sup.1H-NMR.

[0139] The following compounds are prepared analogously to the synthesis of compound Int-1 described:

TABLE-US-00002 Starting material 1 Starting material 2 Product Yield Int-2 [00249] [00250] [00251] 62% Int-3 [00252] [00253] [00254] 52% Int-4 [00255] [00256] [00257] 55% Int-5 [00258] [00259] [00260] 35% Int-6 [00261] [00262] [00263] 40% Int-6a [00264] [00265] [00266] 60% Int-6b [00267] [00268] [00269] 65% Int-6c [00270] [00271] [00272] 55% Int-6d [00273] [00274] [00275] 68% Int-6e [00276] [00277] [00278] 60% Int-6f [00279] [00280] [00281] 57% Int-6g [00282] [00283] [00284] 60% Int-6h [00285] [00286] [00287] 65%

[0140] The following compounds are prepared analogously to the synthesis of compound Int-7 described:

TABLE-US-00003 Starting material 1 Starting material 2 Product Yield Int-8 [00288] [00289] [00290] 80% Int-9 [00291] [00292] [00293] 70% Int-10 [00294] [00295] [00296] 70% Int-11 [00297] [00298] [00299] 79% Int-12 [00300] [00301] [00302] 72% Int-13 [00303] [00304] [00305] 75% Int-14 [00306] [00307] [00308] 80% Int-15 [00309] [00310] [00311] 75% Int-16 [00312] [00313] [00314] 73% Int-17 [00315] [00316] [00317] 70% Int-18 [00318] [00319] [00320] 75% Int-19 [00321] [00322] [00323] 65% Int-20 [00324] [00325] [00326] 58% Int-21 [00327] [00328] [00329] 80% Int-22 [00330] [00331] [00332] 72% Int-23 [00333] [00334] [00335] 75% Int-24 [00336] [00337] [00338] 67% Int-24a [00339] [00340] [00341] 75% Int-24b [00342] [00343] [00344] 70% Int-24c [00345] [00346] [00347] 65% Int-24d [00348] [00349] [00350] 75% Int-24e [00351] [00352] [00353] 80% Int-24f [00354] [00355] [00356] 70% Int-24g [00357] [00358] [00359] 65% Int-24h [00360] [00361] [00362] 78% Int-24i [00363] [00364] [00365] 62% Int-24j [00366] [00367] [00368] 65% Int-24k [00369] [00370] [00371] 70% Int-24l [00372] [00373] [00374] 81% Int-24m [00375] [00376] [00377] 75%

Synthesis of Compound (1-1)

[0141] ##STR00378##

[0142] 11.5 g (31.5 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine and 14.0 g (28.8 mol) of the bromospiro derivative are dissolved in 320 ml of toluene. The solution is degassed and saturated with N.sub.2. 6.8 ml (2.88 mmol) of a 10% tri-tert-butylphosphine solution and 1.32 g (1.44 mmol) of Pd.sub.2(dba).sub.3 are then added, and 9.5 g of sodium tert-butoxide (86.5 mmol) are subsequently added. The reaction mixture is heated at the boil under a protective atmosphere for 5 h. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9% (HPLC). The yield of compound (1-1) is 16.5 g (75% of theory).

Synthesis of Compounds (1-2) to (1-16)

[0143] The following compounds are also prepared analogously to the synthesis of compound (1-1) described in Example 1.

TABLE-US-00004 Starting material 1 Starting material 2 Product Yield 1-2 [00379] [00380] [00381] 78% 1-3 [00382] [00383] [00384] 82% 1-4 [00385] [00386] [00387] 88% 1-5 [00388] [00389] [00390] 67% 1-6 [00391] [00392] [00393] 76% 1-7 [00394] [00395] [00396] 80% 1-8 [00397] [00398] [00399] 78% 1-9 [00400] [00401] [00402] 72% 1-10 [00403] [00404] [00405] 83% 1-11 [00406] [00407] [00408] 75% 1-12 [00409] [00410] [00411] 70% 1-13 [00412] [00413] [00414] 81% 1-14 [00415] [00416] [00417] 65% 1-15 [00418] [00419] [00420] 55% 1-16 [00421] [00422] [00423] 73%

A-2) Example 2: Synthesis of Compounds (2-2) to (2-4)

[0144] ##STR00424##

[0145] 15.0 g (36.9 mmol) of the starting compound are dissolved in 150 ml of acetonitrile, and 5.2 g (29 mmol) of N-bromosuccinimide are added in por-tions at room temperature. When the reaction is complete, water and ethyl acetate are added, and the organic phase is separated off, dried and evaporated. The crude product is subsequently washed by stirring a number of times with hot MeOH/heptane (1:1). Yield: 14.3 g (80%) of the bromospiro derivative Int-25.

[0146] The following brominated compounds are prepared analogously:

TABLE-US-00005 Starting material 1 Brominating reagent Product Yield Int-26 [00425] NBS [00426] 78% Int-27 [00427] 1) nBuLi, −78° C. 2) BrCH.sub.2—CH.sub.2Br [00428] 65% Int-27a [00429] 1) nBuLi, −78° C. 2) I.sub.2 [00430] 75%

Synthesis of Compounds (2-2) to (2-5)

[0147] The following compounds (2-2) to (2-5) are also prepared analogously to the synthesis of compound (1-1) described in Example 1.

TABLE-US-00006 Starting material 1 Starting material 2 Product Yield 2-2 [00431] [00432] [00433] 82% 2-3 [00434] [00435] [00436] 69% 2-4 [00437] [00438] [00439] 88% 2-5 [00440] [00441] [00442] 50%

A-3) Example 3: Synthesis of Compounds 3-1 to 3-3

[0148] ##STR00443##

[0149] 20.0 g (40.1 mmol) of bromine derivative, 9.7 g (40.1 mmol) of 3-phenyl-9H-carbazole and 24 g of Rb.sub.2CO.sub.3 are suspended in 250 ml of p-xylene. 0.95 g (4.2 mmol) of Pd(OAc).sub.2 and 12.6 ml of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 36 h. After cooling, the organic phase is separated off, washed three times with 150 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised three times from toluene and finally sublimed in a high vacuum, giving 15.9 g (24.1 mmol), corresponding to 60% of theory. The purity is 99.9%.

Synthesis of Compounds (3-2) to (3-4)

[0150] The following compounds (3-2) and (3-3) are also prepared analogously to the synthesis of compound (3-1) described in Example 1.

[0151] The following compounds are obtained analogously:

TABLE-US-00007 Starting material 1 Starting material 2 3-2 [00444] [00445] 3-3 [00446] [00447] Product Yield 3-2 [00448] 50% 3-3 [00449] 45%

A-3a) Synthesis of Intermediates for Compounds Under A-4)

[0152] ##STR00450##

[0153] 30 g (74 mmol) of dibenzospirofluorene are initially introduced in 400 ml of THF at −20° C. 49 ml of BuLi (2 M in hexane) are added dropwise at this temperature. After 4 hours, 33 ml (148 mmol) of isopropoxytetramethyl-dioxaborolane are added dropwise. The batch is left to stir overnight at room temperature. When the reaction is complete, water and ethyl acetate are added, and the organic phase is separated off, dried and evaporated. The residue is purified by chromatography on silica gel. Yield: 31 g (59 mmol), 80% of theory, purity according to HPLC>98%.

TABLE-US-00008 Borylating Starting material 1 reagent Product Yield Int-27c [00451] [00452] [00453] 85% Int-27d [00454] [00455] [00456] 80% Int-27e [00457] [00458] [00459] 75%

A-4) Example 4: Synthesis of Compounds 4-1 to 4-13

[0154] ##STR00460##

Spirofluoreneboronic Ester Derivative Int-28

[0155] 50 g (103 mmol) of the bromospirofluorene derivative, 32 g (123 mmol) of bis(pinacolato)diborane and 30 g (309 mmol) of potassium acetate are suspended in 800 ml of dioxane. 2.5 g (3.09 mmol) of 1,1-bis(diphenyl-phosphino)ferrocenepalladium(II) dichloride complex with DCM are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 400 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene (52 g, 95% yield).

[0156] The following compounds are prepared analogously:

TABLE-US-00009 Starting material 1 Product Yield Int-29 [00461] [00462] 90% Int-30 [00463] [00464] 80% Int-31 [00465] [00466] 88% Int-32 [00467] [00468] 88% Int-33 [00469] [00470] 91% Int-34 [00471] [00472] 85% Int-34a [00473] [00474] 80% Int-34b [00475] [00476] 85%

Biphenyl-2-ylbiphenyl-4-yl-(4-chlorophenyl)amine Int-35

[0157] ##STR00477##

[0158] 23.8 g of biphenyl-2-ylbiphenyl-4-ylamine (74 mmol) and 21.2 g of 4-chloroiodobenzene (89 mmol) are dissolved in 500 ml of toluene. The solution is degassed and saturated with N.sub.2. 3 ml (3 mmol) of a 1 M tri-tert-butylphosphine solution and 0.33 g (1.48 mmol) of palladium(II) acetate are then added, and 10.7 g of sodium tert-butoxide (111 mmol) are subsequently added. The reaction mixture is heated at the boil under a protective atmosphere for 12 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene. The yield is 29 g (90% of theory).

[0159] The following compounds are prepared analogously:

TABLE-US-00010 Starting material 1 Starting material 2 Int-36 [00478] [00479] Int-37 [00480] [00481] Int-38 [00482] [00483] Int-39 [00484] [00485] Int-40 [00486] [00487] Int-41 [00488] [00489] Product Yield Int-36 [00490] 78% Int-37 [00491] 80% Int-38 [00492] 81% Int-39 [00493] 92% Int-40 [00494] 85% Int-41 [00495] 75%

Synthesis of Compound (4-1)

[0160] 24.6 g (46.3 mmol) of spirofluorene pinacoleboronic ester derivative and 20.0 g (46.3 mmol) of chlorine derivative are suspended in 300 ml of dioxane and 14.1 g of caesium fluoride (92.6 mmol). 4.1 g (5.56 mmol) of bis-(tricyclohexylphosphine)palladium dichloride are added to this suspension, and the reaction mixture is heated under reflux for 24 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 100 ml of water and subsequently evaporated to dryness. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 29.7 g (80% of theory).

Synthesis of Compounds (4-2) to (4-11) and Int-41a to Int-41c

[0161] The following compounds are also prepared analogously to the synthesis of compound (4-1) described in Example 1.

TABLE-US-00011 Starting material 1 Starting material 2 4-2 [00496] [00497] 4-3 [00498] [00499] 4-4 [00500] [00501] 4-5 [00502] [00503] 4-6 [00504] [00505] 4-7 [00506] [00507] 4-8 [00508] [00509] 4-9 [00510] [00511] 4-10 [00512] [00513] Int-41a [00514] [00515] Int-41b [00516] [00517] Int-41c [00518] [00519] 4-11 [00520] [00521] Product Yield 4-2 [00522] 78% 4-3 [00523] 71% 4-4 [00524] 82% 4-5 [00525] 89% 4-6 [00526] 69% 4-7 [00527] 55% 4-8 [00528] 63% 4-9 [00529] 72% 4-10 [00530] 57% Int-41a [00531] 75% Int-41b [00532] 80% Int-41c [00533] 82% 4-11 [00534] 50%

A-5) Synthesis of Compounds 5-1 to 5-8

Synthesis of Intermediates Int-42 to Int-47

[0162] ##STR00535##

[0163] 27 g (85 mmol) of bisbiphenylamine and 22.0 g (85 mmol) of 1-bromo-fluo-renone are dissolved in 170 ml of toluene. The solution is degassed and saturated with N.sub.2. 4 ml (1.7 mmol) of a 10% tri-tert-butylphosphine solution and 0.2 g (0.89 mmol) of Pd(AcO).sub.2 are then added, and 12.2 g of sodium tert-butoxide (127 mmol) are subsequently added. The reaction mixture Is heated at the boil under a protective atmosphere for 12 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene. The purity is 99% (NMR). The yield is 34 g (80% of theory).

[0164] The following compounds are prepared analogously:

TABLE-US-00012 Starting material 1 Starting material 2 Int-43 [00536] [00537] Int-44 [00538] [00539] Int-45 [00540] [00541] Int-46 [00542] [00543] Int-47 [00544] [00545] Int-48 [00546] [00547] Product Yield Int-43 [00548] 67% Int-44 [00549] 75% Int-45 [00550] 68% Int-46 [00551] 80% Int-47 [00552] 78% Int-48 [00553] 76%

Synthesis of Compounds 5-1 to 5-8

[0165] ##STR00554##

[0166] 16 g (51 mmol) of 4-(2-bromophenyl)dibenzofuran are initially introduced in 80 ml THF at −78° C. 13 ml of BuLi (2 M in hexane) are added dropwise at this temperature. After 1 hour, 24.5 g (47 mmol) of fluoren-9-one in 200 ml THF are added dropwise. The batch is left to stir overnight at room temperature, added to ice-water and extracted with dichloromethane. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed in vacuo, and the residue is, without further purification, heated under reflux at 100° C. overnight with 94 ml of HCl and 1074 ml of AcOH. After cooling, the precipitated solid is filtered off with suction, washed once with 100 ml of water, three times with 100 ml of ethanol each time, recrystallised from heptane and finally sublimed in a high vacuum. Yield: 8.8 g (12 mmol), 59%; purity approx. 99.9% according to HPLC.

[0167] The following compounds are prepared analogously:

TABLE-US-00013 Starting material 1 Starting material 2 5-2 [00555] [00556] 5-3 [00557] [00558] 5-4 [00559] [00560] 5-5 [00561] [00562] 5-6 [00563] [00564] 5-7 [00565] [00566] 5-8 [00567] [00568] 5-9 [00569] [00570] Product Yield 5-2 [00571] 55% 5-3 [00572] 67% 5-4 [00573] 70% 5-5 [00574] 49% 5-6 [00575] 60% 5-7 [00576] 58% 5-8 [00577] 65% 5-9 [00578] 70%

B) Device Examples

[0168] OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 04/058911, which is adapted to the circumstances described here (for example materials).

[0169] The data of various OLEDs are presented in the following device examples E1 to E13 and E16 to E18 (Inventive examples) and V1 to V4 (comparative examples). The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs have in princi-ple the following layer structure: substrate/p-doped hole-transport layer (HIL1)/hole-transport layer (HTL)/p-doped hole-transport layer (HIL2)/hole-transport layer (EBL)/emission layer (EML)/electron-transport layer (ETL)/electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm.

[0170] The materials required for the production of the OLEDs are shown in Table 1, the various component structures are shown in Table 2.

[0171] All materials are applied by thermal vapour deposition in a vacuum cham-ber. 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 the matrix materials in a certain proportion by volume by co-evaporation. An expression such as H1:SEB (95%:5%) here means that material H1 is present in the layer in a proportion by volume of 95% and SEB is present in the layer in a proportion of 5%. Analogously, the electron-transport layer or the hole-injection layers may also consist of a mixture of two materials.

[0172] 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 percent) 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 term EQE @ 10 mA/cm.sup.2 denotes the external quantum efficiency at a current density of 10 mA/cm.sup.2. LT80 @60 mA/cm.sup.2 is the lifetime by which the OLED has dropped to 80% of the initial intensity at a constant current of 60 mA/cm.sup.2.

TABLE-US-00014 TABLE 1 Structures of the materials used [00579] F4TCNQ [00580] HIM [00581] H1 [00582] SEB [00583] H2 [00584] TEG [00585] ETM [00586] LiQ [00587] NPB [00588] HTMV1 [00589] HTM1 [00590] HTM2 [00591] HTM3 [00592] HTM4 [00593] HTM5 [00594] HTM8 [00595] HTM9 [00596] HTM10

TABLE-US-00015 TABLE 2 Structure of the OLEDs HTL EBL EML EIL HIL1 Thickness/ HIL2 Thickness/ Thickness/ ETL Thickness/ Exp. Thickness/nm nm Thickness/nm nm nm Thickness/nm nm V1 HIM: F4TCNQ(5%) HIM NPB: F4TCNQ(5%) NPB H1: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm V2 HIM: F4TCNQ(5%) HIM HTMV1: F4TCNQ(5%) HTMV1 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E1 HIM: F4TCNQ(5%) HIM HTM1: F4TCNQ(5%) HTM1 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E2 HIM: F4TCNQ(5%) HIM HTM2: F4TCNQ(5%) HTM2 H1: SEB1(5%) ETM: LiQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E3 HIM: F4TCNQ(5%) HIM HTM3: F4TCNQ(5%) HTM3 H1: SEB1(5%) ETM: LIQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E4 HIM: F4TCNQ(5%) HIM HTM4: F4TCNQ(5%) HTM4 H1: SEB1(5%) ETM: LIQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E5 HIM: F4TCNQ(5%) HIM HTM5: F4TCNQ(5%) HTM5 H1: SEB1(5%) ETM: LIQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E6 HIM: F4TCNQ(5%) HIM HTM8: F4TCNQ(5%) HTM8 H1: SEB1(5%) ETM: LIQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E7 HIM: F4TCNQ(5%) HIM HTM9: F4TCNQ(5%) HTM9 H1: SEB1(5%) ETM: LIQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm E8 HIM: F4TCNQ(5%) HIM HTM10: F4TCNQ(5%) HTM10 H1: SEB1(5%) ETM: LIQ(50%) LiQ 20 nm 155 nm 20 nm 20 nm 20 nm 30 nm 1 nm V3 HIM: F4TCNQ(5%) HIM NPB: F4TCNQ(5%) NPB H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm V4 HIM: F4TCNQ(5%) HIM HTMV1: F4TCNQ(5%) HTMV1 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E9 HIM: F4TCNQ(5%) HIM HTM1: F4TCNQ(5%) HTM1 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E10 HIM: F4TCNQ(5%) HIM HTM2: F4TCNQ(5%) HTM2 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E11 HIM: F4TCNQ(5%) HIM HTM3: F4TCNQ(5%) HTM3 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E12 HIM: F4TCNQ(5%) HIM HTM4: F4TCNQ(5%) HTM4 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E13 HIM: F4TCNQ(5%) HIM HTM5: F4TCNQ(5%) HTM5 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E16 HIM: F4TCNQ(5%) HIM HTM8: F4TCNQ(5%) HTM8 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E17 HIM: F4TCNQ(5%) HIM HTM9: F4TCNQ(5%) HTM9 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm E18 HIM: F4TCNQ(5%) HIM HTM10: F4TCNQ(5%) HTM10 H2: TEG(10%) ETM: LIQ(50%) LiQ 20 nm 210 nm 20 nm 20 nm 30 nm 40 nm 1 nm

[0173] Compounds HTM1 to HTM5 and HTM8 to HTM10 according to the invention are very highly suitable for use as OLED materials, as shown by Examples E1 to E13 and E16 to E18 (E1 to E8: singlet components; E9 to E13 and E16 to E18: triplet components). Improved performance data of the OLEDs are obtained with the compounds compared with the reference compounds HTMV1 and NPB (Comparative Examples V1 and V2: singlet components; V3 and V4: triplet components).

[0174] In a singlet blue component, samples E2 (7.9%), E3 (8.6%), E4 (7.9%) and E5 (8.3%) according to the invention exhibit higher quantum efficiencies at 10 mA/cm.sup.2 compared with reference samples V1 and V2 (6.2% and 7.7%). The lifetime LT80 at 60 mA/cm.sup.2 in the case of samples E1 (356 h), E2 (312 h), E4 (403 h), E6 (275 h), E7 (316 h) and E8 (408 h) according to the invention is also significantly better than in the case of reference samples V1 (125 h) and V2 (257 h).

[0175] In a triplet green component, reference samples V3 (11.7%) and V4 (18.6%) exhibit lower or the same quantum efficiencies at 2 mA/cm.sup.2 than samples E10 (18.6%), E12 (19.8%), E16 (19.6%), E17 (19.4%) and E18 (18.6%) according to the invention. The lifetimes (80%) at 20 mA/cm.sup.2 of samples E9 (220 h), E10 (96 h), E11 (109 h), E12 (172 h), E13 (111 h), E16 (150 h), E17 (144 h) and E18 (160 h) according to the invention are also greater than in the case of reference samples V3 (80 h) and V4 (84 h).