Compounds for electronic devices

Abstract

The present invention relates to compounds which are suitable for use in electronic devices, preferably organic electroluminescent devices.

Claims

1. A compound of formula (I-1) or (III-1): ##STR00433## wherein Ar.sup.1 is on each occurrence, identically or differently, selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, triphenylenyl, chrysenyl, biphenyl, terphenyl, fluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl or silafluorenyl, each of which is optionally substituted by one or more radicals R.sup.1; R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, 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 or alkynyl group having 2 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2 and wherein one or more CH.sub.2 groups is optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CS, CNR.sup.2, C(O)O, C(O)NR.sup.2, NR.sup.2, P(O)(R.sup.2), O, S, SO, or SO.sub.2 and wherein one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, and wherein two or more radicals R.sup.1 optionally define a ring with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, NO.sub.2, P(O)(R.sup.3).sub.2, S(O)R.sup.3, S(O).sub.2R.sup.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 or alkynyl group having 2 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.3 and wherein one or more CH.sub.2 groups is optionally replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CS, CNR.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 and wherein one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, and wherein two or more radicals R.sup.2 optionally define a ring system with one another; R.sup.3 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic, or heteroaromatic organic radical having 1 to 20 C atoms, wherein one or more H atoms is optionally replaced by D or F; and wherein two or more radicals R.sup.3 optionally define a ring system with one another; X is C(R.sup.1).sub.2; and m, n, o, p, q, and r are on each occurrence, identically or differently, 0 or 1; wherein when any one of m, n, o, p, q and r is 0, a group R.sup.1 is bonded instead at the relevant positions to which the corresponding group X is bonded; and wherein the sum of m and n is 1, and the sum of o and p is 1, and the sum of q and r is 1.

2. The compound of claim 1, wherein R.sup.1 is on each occurrence, identically or differently, H, D, F, CN, Si(R.sup.2).sub.3, a straight-chain alkyl group having 1 to 8 C atoms, or a branched or cyclic alkyl group having 3 to 8 C atoms, wherein the alkyl groups are optionally substituted by one or more radicals R.sup.2 and wherein one or more CH.sub.2 groups is optionally replaced by CC, R.sup.2CCR.sup.2, Si(R.sup.2).sub.2, CO, or O, or an aryl or heteroaryl group having 6 to 16 aromatic ring atoms optionally substituted by one or more radicals R.sup.2.

3. An oligomer, polymer, or dendrimer comprising one or more compounds of claim 1, wherein the bond(s) to the polymer, oligomer or dendrimer are located at any desired positions in formulae (I-1) or (III-1) which are substituted by R.sup.1 or R.sup.2.

4. A formulation comprising at least one polymer, oligomer, or dendrimer of claim 3 and at least one solvent.

5. An electronic device 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, light-emitting electrochemical cells, organic laser diodes, and organic electroluminescent devices, wherein said electronic device comprises at least one polymer, oligomer or dendrimer of claim 3.

6. The electronic device of claim 5, wherein said electronic device is an organic electroluminescent device and said at least one polymer, oligomer or dendrimer is employed as emitting material in an emitting layer.

7. A formulation comprising at least one compound of claim 1 and at least one solvent.

8. An electronic device 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, light-emitting electrochemical cells, organic laser diodes, and organic electroluminescent devices, wherein said electronic device comprises at least one compound of claim 1.

9. The electronic device of claim 8, wherein said electronic device is an organic electroluminescent devices and said at least one compound is employed as emitting material in an emitting layer.

10. A process for preparing the compound of claim 1, wherein one or more organometallic coupling processes is employed.

Description

WORKING EXAMPLES

A) Synthesis Examples

(1) 4-Bromotoluene and diphenylamine are commercially available. The synthesis of diethyl 2-chloro-5-naphthalen-1-ylterephthalate is described in WO 2010/012328 A1.

(2) A-1) Variant I

Synthesis of 7,7,13,13-tetramethyl-N-(7,7,13,13-tetramethyl-7,13-dihydrobenzo[g]indeno[1,2-b]fluoren-11-yl)-N-(p-tolyl)-7,13-dihydrobenzo[g]indeno[1,2-b]fluoren-11-amine (I)

(3) ##STR00095## ##STR00096##

(4-Methylphenyl)diphenylamine (Ia)

(4) Besides the synthesis described here, further syntheses which are described in the literature are available to the person skilled in the art. Diphenylamine (88.34 g, 520 mmol) and 4-bromotoluene (82.0 g, 470 mmol) are dissolved in 900 ml of toluene. Tri-ortho-tolylphosphine (1.46 g, 4.7 mmol), palladium(II) acetate (0.53 g, 2.4 mmol) and sodium tert-butoxide (69.1 g, 700 mmol) are subsequently added to the reaction solution, which is then heated under reflux for 3 days. The mixture is extended with toluene and dist. H.sub.2O at room temperature, the organic phase is separated off, and the aqueous phase is extracted a number of times with toluene. The org. phase is dried using MgSO.sub.4, filtered through AlOx and evaporated. The residue is brought to precipitation using heptane and recrystallised from isopropanol, giving (4-methylphenyl)diphenylamine as a colourless solid (85.7 g, 70% of theory).

(5) The following compounds are prepared analogously:

(6) TABLE-US-00004 Amine Bromoarene Product Yield 65% 00 01 02 75% 03 04 05 62% 06 07 08 68%

Bis-(4-bromophenyl)-p-tolylamine (Ib)

(7) (4-Methylphenyl)diphenylamine (85.2 g, 330 mmol) is dissolved in 1 l of DCM and cooled to 0 C. N-Bromosuccinimide (117 g, 660 mmol) is added in small portions with stirring at such a rate that the reaction temperature does not exceed 5 C. The reaction mixture is warmed to room temperature in an ice bath overnight. 500 ml of a 10% Na.sub.2SO.sub.3 solution are then added, and the phases are separated. The aqueous phase is extracted a number of times with DCM. The organic phase is washed with dist. H.sub.2O, dried and freed from solvent. The solid obtained is recrystallised a number of times from 1-butanol, giving 129 g of a colourless solid (94% of theory).

4-Methyl-N,N-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenylaniline (Ic)

(8) Bis-(4-bromophenyl)-p-tolylamine (128 g, 310 mmol) and bispinacolatodiborane (195 g, 770 mmol) are dissolved in 1.5 l of THF. Potassium acetate (241 g, 2460 mmol) and 1,1-bis(diphenylphosphino)ferrocene-palladium(II) dichloride*DCM (7.52 g, 9.2 mmol) are then added to the reaction solution, which is then heated under reflux for six days. After cooling to room temperature, the batch is extended with DCM and dist. H.sub.2O, and the aqueous phase is extracted a number of times with DCM. The combined organic phases are washed with dist. H.sub.2O and, after drying using MgSO.sub.4, filtered through AlOx. The solvent is removed at atmospheric pressure. The solid obtained is washed with heptane and acetonitrile, giving 110 g of a pale-grey powder (70% of theory).

Tetraethyl 4,4-(p-tolylazandiyl)bis(4-(naphthalen-1-yl)-[1,1-biphenyl]-2,5-dicarboxylate)

(9) 4-Methyl-N,N-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylaniline (110 g, 215 mmol) and diethyl 2-chloro-5-naphthalen-1-ylterephthalate (189 g, 495 mmol) are dissolved in 1.2 l of toluene, and tetrakis-(triphenylphosphine)palladium (4.97 g, 4.3 mmol) and 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl (3.53 g, 8.6 mmol) are added. Tetraethylammonium hydroxide (20% in H.sub.2O) (450 ml, 645 mmol) is subsequently added to the reaction solution. The batch is heated under reflux for seven hours, cooled to room temperature and extended with dist. H.sub.2O. After phase separation, the aqueous phase is extracted a number of times with toluene. The combined organic phases are washed with dist. H.sub.2O, dried over MgSO.sub.4 and filtered through AlOx. The organic phase is evaporated to give a dark-orange viscous oil and purified by chromatography (silica gel, heptane/THF 85:15), giving 147 g (72% of theory) of tetraethyl 4,4-(p-tolylazandiyl)bis(4-(naphthalen-1-yl)-[1,1-biphenyl]-2,5-dicarboxylate) in the form of an intensely yellow solid.

(10) The following compounds are prepared analogously:

(11) TABLE-US-00005 Terephthalic Boronic acid acid ester ester derivative Product Yield 09 0 69% as above 76% as above 74% as above 68%

(12) The following compound can be prepared analogously:

(13) TABLE-US-00006 Terephthalic acid Boronic acid ester ester derivative Product 0

2-[4-{[2,5-Bis-(1-hydroxy-1-methylethyl)-4-naphthalen-1-ylbiphenyl-4-yl]-p-tolylamino}-5-(1-hydroxy-1-methylethyl)-4-naphthalen-1-yl-biphenyl-2-yl]propan-2-ol (Ie)

(14) Tetraethyl 4,4-(p-tolylazandiyl)bis(4-(naphthalen-1-yl)-[1,1-biphenyl]-2,5-dicarboxylate) (147 g, 154 mmol) is dissolved in 750 ml of THF, and methylmagnesium chloride (20% solution in THF) (617 ml, 1700 mmol) is added at 0 C. The reaction solution is allowed to warm to room temperature in an ice bath overnight. The batch is carefully hydrolysed using saturated NH.sub.4Cl solution and neutralised using 4% hydrochloric acid. The mixture is extended with dist. H.sub.2O and extracted thoroughly with toluene. The combined organic phases are washed a number of times with dist. H.sub.2O and once with NaHCO.sub.3 solution and dried over MgSO.sub.4. After removal of the solvent in vacuo, a pale-beige solid is obtained. This is washed with a heptane/isopropanol mixture, giving 136 g (98% of theory) of 2-[4-{[2,5-bis-(1-hydroxy-1-methylethyl)-4-naphthalen-1-ylbiphenyl-4-yl]-p-tolylamino}-5-(1-hydroxy-1-methylethyl)-4-naphthalen-1-ylbiphenyl-2-yl]propan-2-ol as a colourless solid.

7,7,13,13-Tetramethyl-N-(7,7,13,13-tetramethyl-7,13-dihydrobenzo[g]-indeno[1,2-b]fluoren-11-yl)-N-(p-tolyl)-7,13-dihydrobenzo[g]indeno-[1,2-b]fluoren-11-amine (I) (Synthesis Example 1)

(15) ##STR00121##

(16) 2-[4-{[2,5-Bis-(1-hydroxy-1-methylethyl)-4-naphthalen-1-ylbiphenyl-4-yl]-p-tolylamino}-5-(1-hydroxy-1-methylethyl)-4-naphthalen-1-ylbiphenyl-2-yl]-propan-2-ol (135 g, 151 mmol) is dissolved in 1.3 l of DCM, and methanesulfonic acid (69 ml, 1060 mmol) and polyphosphoric acid (156 g, 1350 mmol) are added at 20 C. The reaction solution is allowed to warm to room temperature overnight. The yellow solid which precipitates is filtered off and purified by Soxhlett extraction and subsequent sublimation, giving 47.4 g of a yellow solid (38% of theory).

(17) The following compounds are prepared analogously:

(18) TABLE-US-00007 Synthesis Example Structure Yield 2 44% 3 42% 4 39% 5 34%

(19) The following compound can be prepared analogously:

(20) TABLE-US-00008 Synthesis Example Structure 6

(21) A-2) Variant II

(22) ##STR00127##

7,7,13,13-Tetramethyl-5-phenyl-7,13-dihydrobenzo[g]indeno[1,2-b]-fluorene (IIa)

(23) 12.8 g (103 mmol) of benzeneboronic acid, 37.7 g (86 mmol) of 5-bromo-7,7,13,13-tetramethyl-7,13-dihydrobenzo[g]indeno[1,2-b]fluorene and 29.7 g (215 mmol) of K.sub.2CO.sub.3 are suspended in 500 ml of toluene/water (1:1). 0.99 g (0.86 mmol) of tetrakis(triphenylphosphine)palladium is added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the reaction mixture is diluted with ethyl acetate, the organic phase is separated off, 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. The yield is 29.2 g (78% of theory).

(24) The following compounds are prepared analogously:

(25) TABLE-US-00009 Starting Starting material 1 material 2 Product Yield 0 74% 69% 79% 73% 0 67% 59% 81%

11-Bromo-7,7,13,13-tetramethyl-5-phenyl-7,13-dihydrobenzo[g]-indeno[1,2-b]fluorene (IIb)

(26) 29.2 g (67 mmol) of 7,7,13,13-tetramethyl-5-phenyl-7,13-dihydrobenzo-[g]indeno[1,2-b]fluorene (IIa) are dissolved in 500 ml of CHCl.sub.3, and 10.8 g (67 mmol) of bromine, dissolved in 500 ml of CHCl.sub.3, are slowly added at 10 C. When the reaction is complete, water is added, the organic phase is separated off, dried and evaporated. The crude product is subsequently washed by stirring a number of times with hot heptane/toluene (5:1). Yield: 30.5 g (89%) of the product as a white solid.

(27) The following compounds are prepared analogously:

(28) TABLE-US-00010 Starting material 1 Product Yield 0 83% 75% 81% 62% 72% 0 44% 87%

7,7,13,13-Tetramethyl-5-phenyl-N,N-di-p-tolyl-7,13-dihydrobenzo-[g]indeno[1,2-b]fluoren-11-amine (II) (Synthesis Example 7)

(29) ##STR00163##

(30) 9.74 g of di-p-tolylamine (49.4 mmol), 11-bromo-7,7,13,13-tetramethyl-5-phenyl-7,13-dihydrobenzo[g]indeno[1,2-b]fluorene (IIb) (41.1 mmol) are dissolved in 500 ml of toluene. The solution is degassed and saturated with argon. 2.5 ml (2.5 mmol) of a 1 M tri-tert-butylphosphine solution and 0.355 g (1.23 mmol) of palladium(II) acetate are then added. 11.9 g of sodium tert-butoxide (124 mmol) are subsequently added. The reaction mixture is heated at the boil for 12 h under a protective-gas atmosphere. Water is subsequently added to the mixture, the organic phase is washed three times with water, 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%. The yield is 15.2 g (58% of theory).

(31) The following compounds are prepared analogously:

(32) TABLE-US-00011 Starting Ex. Starting material 1 material 2 Product Yield 8 69% 9 78% 10 0 72% 11 83% 12 76% 13 0 67% 14 75% 15 81% 16 0 58% 17 73% 18 61% 19 68% 20 00 01 02 72% 21 03 04 05 81% 22 06 07 08 79% 23 09 0 77% 24 64% 25 77% 26 0 84% 27 72% 28 68% 29 81% 30 0 79% 31 73% 32 77% 33 0 82% 34 77% 35 65% 36 0 79%

(33) A-3) Variant III

(34) III-1) Synthesis of Building Blocks (i)

(35) General Reaction Scheme:

(36) ##STR00251##

Ethyl 1-(9,9-dimethyl-9H-fluoren-2-yl)-2-naphthoate (i-a)

(37) Methyl 1-bromonaphthalene-2-carboxylate (150 g, 563 mmol), 9,9-dimethyl-9H-fluoren-2-ylboronic ester (148.9 g, 619 mmol) and potassium phosphate monohydrate (286 g, 1.182 mol) are dissolved in a mixture of 1.2 l of toluene and 1 l of water, and palladium acetate (1.28 g, 5.6 mmol) and tri-ortho-tolylphosphine (3.5 g, 11.3 mmol) are added. The batch is heated under reflux overnight, cooled to room temperature and extended with dist. water. After phase separation, the aqueous phase is extracted a number of times with toluene. The combined organic phases are washed with dist. water, dried over magnesium sulfate and filtered through aluminium oxide. The organic phase is evaporated to an orange oil, giving 213 g of product (99% of theory).

Ethyl 1-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-2-naphthoate (i-b)

(38) (i-a) (122 g, 295 mmol) is dissolved in 1 l of chloroform and cooled to 0 C. A dibromine solution (14.4 ml, 280 mmol) in 0.5 l of chloroform is added dropwise with stirring at such a rate that the reaction temperature does not exceed 5 C. The reaction mixture is warmed to room temperature in an ice bath overnight. 500 ml of a 10% sodium thiosulfate solution are added, and the phases are separated. After phase separation, the aqueous phase is extracted a number of times with chloroform. The combined organic phases are washed with dist. water, dried over magnesium sulfate and filtered through aluminium oxide. The organic phase is evaporated to a colourless oil, giving 128 g of product (95% of theory).

2-(1-(7-Bromo-9,9-dimethyl-9H-fluoren-2-yl)naphthalen-2-yl)propan-2-ol (i-c)

(39) (i-b) (80 g, 175 mmol) and cerium(III) chloride (48 g, 247 mmol) are dissolved in 800 ml of THF, and methylmagnesium chloride (3 M solution in THF) (146 ml, 437 mmol) is added at 0 C. The reaction solution is allowed to warm to room temperature in an ice bath overnight. The batch is carefully hydrolysed using saturated NH.sub.4Cl solution and neutralised using 4% hydrochloric acid. The mixture is extended with dist. water and extracted thoroughly with toluene. The combined organic phases are washed a number of times with dist. water and once with sodium hydrogencarbonate solution and dried over magnesium sulfate. After removal of the solvent in vacuo, a pale-beige solid is obtained. This is recrystallised from a heptane/toluene mixture, giving 69 g (86% of theory) as a colourless solid.

11-Bromo-7,7,13,13-tetramethyl-7,13-dihydrobenzo[g]indeno[1,2-b]-fluorene (i)

(40) (i-c) (61 g, 133 mmol) is dissolved in 300 ml of DCM, and methanesulfonic acid (60 ml, 933 mmol) and polyphosphoric acid (91 g, 933 mmol) are added at 0 C. The reaction solution is allowed to warm to room temperature overnight. The mixture is extended with ethanol and evaporated. The residue is dissolved in toluene, washed with NaOH solution and dist. water and dried over magnesium sulfate. After removal of the solvent in vacuo, the solid is recrystallised from ethanol, giving 55 g of a yellow solid (93% of theory).

(41) The following compounds are prepared analogously:

(42) TABLE-US-00012 Yield Starting material 1 Product (4 steps) 68% 59% 64% 74%

(43) III-2) Synthesis of Building Block (ii-1)

(44) General Reaction Scheme:

(45) ##STR00260##

Methyl 1-phenylnaphthalene-2-carboxylate (ii-a)

(46) Methyl 1-bromonaphthalene-2-carboxylate (70.0 g, 264 mmol), phenylboronic acid (38.6 g, 317 mmol) and potassium phosphate monohydrate (182 g, 792 mmol) are dissolved in a mixture of 0.2 l of toluene, 0.2 l of dioxane and 0.2 l of water, and palladium acetate (1.18 g, 5.3 mmol) and tri-ortho-tolylphosphine (3.2 g, 10.6 mmol) are added. The batch is heated under reflux overnight, cooled to room temperature and extended with dist. water. After phase separation, the aqueous phase is extracted a number of times with toluene. The combined organic phases are washed with dist. water, dried over magnesium sulfate and filtered through aluminium oxide. The organic phase is evaporated to an orange oil, giving 69 g of product (99% of theory).

2-(1-Phenylnaphthalen-2-yl)propan-2-ol (ii-b)

(47) (ii-a) (69 g, 264 mmol) and cerium(III) chloride (71 g, 291 mmol) are dissolved in 500 ml of THF, and methylmagnesium chloride (3 M solution in THF) (308 ml, 925 mmol) is added at 0 C. The reaction solution is allowed to warm to room temperature in an ice bath overnight. The batch is carefully hydrolysed using saturated NH.sub.4Cl solution and neutralised using 4% hydrochloric acid. The mixture is extended with dist. water and extracted thoroughly with toluene. The combined organic phases are washed a number of times with dist. water and once with sodium hydrogencarbonate solution and dried over magnesium sulfate. After removal of the solvent in vacuo, a pale-beige solid is obtained. This is recrystallised from a heptane/toluene mixture, giving 52 g (75% of theory) as a colourless solid.

7,7-Dimethyl-7H-benzo[c]fluorene (ii-1)

(48) (ii-b) (52 g, 198 mmol) is dissolved in 500 ml of DCM, and methanesulfonic acid (64 ml, 991 mmol) and polyphosphoric acid (77 g, 793 mmol) are added at 0 C. The reaction solution is allowed to warm to room temperature overnight. The mixture is extended with ethanol and evaporated. The residue is dissolved in toluene, washed with NaOH solution and dist. water and dried over magnesium sulfate. After removal of the solvent in vacuo, the solid is recrystallised from ethanol, giving 44 g of a yellow solid (91% of theory).

(49) III-3) Synthesis of Building Block (ii-2)

(50) ##STR00261##

Diphenyl(1-phenylnaphthalen-2-yl)methanol (ii-c)

(51) (ii-a) (35 g, 133 mmol) and cerium(III) chloride (36 g, 146 mmol) are dissolved in 250 ml of THF, and phenylmagnesium chloride (3 M solution in THF) (150 ml, 450 mmol) is added at 0 C. The reaction solution is allowed to warm to room temperature in an ice bath overnight. The batch is carefully hydrolysed using saturated NH.sub.4Cl solution and neutralised using 4% hydrochloric acid. The mixture is extended with dist. water and extracted thoroughly with toluene. The combined organic phases are washed a number of times with dist. water and once with sodium hydrogencarbonate solution and dried over magnesium sulfate. After removal of the solvent in vacuo, a pale-beige solid is obtained. This is recrystallised from heptane/toluene, giving 41 g (80% of theory) as a colourless solid.

(52) Building block (ii-2) is synthesised analogously to (ii-1), with a yield of 88%.

(53) III-4) Synthesis of Building Block (ii-3)

(54) ##STR00262##

(55) 7H-Benzo[c]fluorene is synthesised in accordance with the following literature procedure: Organic Letters, 2009, Vol. 11, No. 20, 4588-4591

(56) Synthesis of (ii-3)

(57) 7H-Benzo[c]fluorene (38 g, 176 mmol), 1,5-dibromopentane (40.5 g, 176 mmol) and tetrabutylammonium bromide (32.3 g, 100 mmol) are dissolved in 0.5 l of toluene. 0.5 l of 3 M NaOH solution is added, and the reaction mixture is boiled under reflux overnight. The reaction mixture is cooled to room temperature, the phases are separated, the aqueous phase is extracted three times with toluene. The organic phase is washed with dist. water, dried and freed from solvent. The solid obtained is recrystallised from toluene/heptane, giving 31 g of a colourless solid (62% of theory).

(58) III-5) Synthesis of Building Block (iii)

(59) ##STR00263##

5-Bromo-7,7-dimethyl-7H-benzo[c]fluorene (iii-a)

(60) (ii-1) (38.2 g, 156 mmol) is dissolved in 0.3 l of chloroform and cooled to 0 C. A dibromine solution (117 g, 660 mmol) in 0.2 l of chloroform is added dropwise with stirring at such a rate that the reaction temperature does not exceed 5 C. The reaction mixture is warmed to room temperature in an ice bath overnight. 200 ml of a 10% sodium thiosulfate solution are added, and the phases are separated. The aqueous phase is extracted a number of times with DCM. The organic phase is washed with dist. water, dried and freed from solvent. The solid obtained is recrystallised from toluene/heptane, giving 50 g of a colourless solid (99% of theory).

7,7-Dimethyl-5-phenyl-7H-benzo[c]fluorene (iii-b)

(61) (ii-a) (28.5 g, 88 mmol), phenylboronic acid (13.2 g, 106 mmol) and potassium carbonate (30.5 g, 220 mmol) are dissolved in a mixture of 150 ml of toluene and 150 ml of water, and tetrakis(triphenylphosphine)palladium (1.02 g, 0.9 mmol) is added. The batch is heated under reflux overnight, cooled to room temperature and extended with dist. water. After phase separation, the aqueous phase is extracted a number of times with toluene. The combined organic phases are washed with dist. water, dried over magnesium sulfate and filtered through AlOx and silica gel. The organic phase is evaporated, and the resultant solid is washed with ethanol, giving 25.9 g (92% of theory) of product.

9-Bromo-7,7-dimethyl-5-phenyl-7H-benzo[c]fluorene (iii)

(62) (iii-b) (25.8 g, 81 mmol) is dissolved in 0.15 l of chloroform and cooled to 0 C. A dibromine solution (13.6 g, 85 mmol) in 0.1 l of chloroform is added dropwise with stirring at such a rate that the reaction temperature does not exceed 5 C. The reaction mixture is warmed to room temperature in an ice bath overnight. 100 ml of a 10% sodium thiosulfate solution are added, and the phases are separated. The aqueous phase is extracted a number of times with DCM. The organic phase is washed with dist. water, dried and freed from solvent. The solid obtained is recrystallised from-toluene/heptane, giving 22 g of a colourless solid (62% of theory).

(63) The following compounds are prepared analogously:

(64) TABLE-US-00013 Starting material ii Boronic acid Yield or analogue ArB(OH).sub.2 Product (iii analogue) (3 steps) 66% 65% 0 70% 61% 53% 0 61% 37% 64% 0 31% 50% 54% 34% 00 01 02 58%

(65) III-6) Synthesis of Building Blocks (iv)

(66) General Reaction Scheme:

(67) ##STR00303##

N-Phenyl-7,7,13,13-tetramethyl-7,13-dihydrobenzo[g]indeno[1,2-b]-fluoren-11-amine (iv)

(68) i (37 g, 84.2 mmol) and aniline (8.6 g, 92.6 mmol) are dissolved in 500 ml of toluene. The solution is degassed and saturated with argon. 4.1 g (5.1 mmol) of Pd(dppf)Cl.sub.2 are then added. 24.3 g of sodium tert-butoxide (253 mmol) are subsequently added. The reaction mixture is heated at the boil for 12 h under a protective-gas atmosphere. Water is subsequently added to the mixture, the organic phase is washed three times with water, 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 yield is 31 g (77% of theory).

(69) TABLE-US-00014 Starting material i or analogue Amine Product iv analogue Yield 04 05 06 58% 07 08 09 72% 0 62% 51% 63% 0 39% 57% 59% 0 64% 32% 61% 64% 0 68% 39% 65% 0 58% 52% 66% 0 46% 72% 64% 33% 0 54% 47% 41%

(70) III-7) Synthesis of Target Compounds (III)

(71) General Reaction Scheme:

(72) ##STR00379##

7,7,13,13-Tetramethyl-N-(7,7-dimethyl-5-phenyl-7H-benzo[c]fluoren-9-yl)-N-phenyl-7,13-dihydrobenzo[g]indeno[1,2-b]fluoren-11-amine (III)

Synthesis Example 37

(73) iv (20 g, 44.3 mmol) and iii (18.6 g, 46.5 mmol) are dissolved in 500 ml of toluene. The solution is degassed and saturated with argon. 2.5 ml (2.5 mmol) of a 1 M tri-tert-butylphosphine solution and 0.355 g (1.23 mmol) of palladium(II) acetate are then added. 11.9 g of sodium tert-butoxide (124 mmol) are subsequently added. The reaction mixture is heated at the boil for 12 h under a protective-gas atmosphere. Water is subsequently added to the mixture, the organic phase is washed three times with water, 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%. The yield is 21 g (62% of theory).

(74) The following compounds are prepared analogously:

(75) TABLE-US-00015 Starting material iv Starting material iii Ex. or analogue or analogue 38 0 39 40 41 42 43 0 44 45 46 47 48 00 01 49 02 03 50 04 05 Ex. Product III analogue Yield 38 06 74% 39 07 81% 40 08 69% 41 09 75% 42 0 52% 43 58% 44 33% 45 79% 46 54% 47 81% 48 44% 49 63% 50 71%

B) Device Examples: Production of OLEDs

(76) 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 (layer-thickness variation, materials).

(77) The data for various OLEDs are presented in the following examples (see Tables 1 to 3). The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs have in principle the following layer structure: substrate/buffer (20 nm)/hole-injection layer (HIL, 5 nm)/hole-transport layer (HTL, 30 nm)/emission layer (EML, 20 nm)/electron-transport layer (ETL, 30 nm)/electron-injection layer (LiQ 1 nm) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. A layer of Clevios P VP Al 4083 (purchased from Heraeus Clevios GmbH, Leverkusen) with a thickness of 20 nm is applied as buffer by spin coating. All remaining materials are applied by thermal vapour deposition in a vacuum chamber. The structure of EML and ETL of the OLEDs is shown in Table 1. The materials used are shown in Table 3.

(78) The emission layer (EML) always consists of at least one matrix material (host=H) and an emitting dopant (dopant=D), which is admixed with the matrix material in a certain proportion by volume by co-evaporation. An expression such as H1:D1 (95%:5%) here means that material H1 is present in the layer in a proportion by volume of 95% and D1 is present in the layer in a proportion of 5%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(79) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra are recorded, the current efficiency (measured in cd/A) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density are calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics, and finally the lifetime of the components is determined. The electroluminescence spectra are recorded at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The expression EQE @ 1000 cd/m.sup.2 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. The lifetime LT50 @ 60 mA/cm.sup.2 is the time which passes until the initial luminance (cd/m.sup.2) at a current density of 60 mA/cm.sup.2 has dropped to half. The data obtained for the various OLEDs are summarised in Table 2.

(80) Use of Compounds According to the Invention as Dopants in Fluorescent OLEDs

(81) Compounds according to the invention are particularly suitable as blue fluorescent dopants. The comparative dopants used are dopants V-D1 and V-D2 known from the prior art (WO 2006/108497 and WO 2008/006449). Dopants D3, D4, D5, D6 and D7 are measured as examples according to the invention.

(82) TABLE-US-00016 TABLE 1 Structure of the OLEDs EML ETL Ex. Thickness/nm Thickness /nm V1 H1(95%):V-D1(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm V2 H3(95%):V-D1(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm V3 H1(95%):V-D2(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm V4 H3(95%):V-D2(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E5 H1(95%):D3(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E6 H2(95%)D3(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E7 H1(95%):D4(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E8 H3(95%):D4(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E9 H1(95%):D5(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E10 H2(95%)D5(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E11 H1(95%):D6(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E12 H3(95%):VD6(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm E13 H1(95%):D7(5%) 20 nm ETM1(50%):LiQ(50%) 30 nm

(83) TABLE-US-00017 TABLE 2 Data for the OLEDs EQE LT50 @ @ 1000 cd/m.sup.2 60 mA/cm.sup.2 CIE Ex. % [h] x y V1 2.4 110 0.16 0.09 V2 2.3 120 0.16 0.10 V3 2.6 260 0.15 0.17 V4 2.5 280 0.15 0.18 E5 6.2 560 0.14 0.10 E6 6.4 620 0.14 0.11 E7 6.9 580 0.14 0.12 E8 7.1 600 0.14 0.13 E9 6.5 560 0.13 0.10 E10 6.8 610 0.13 0.11 E11 5.2 450 0.13 0.08 E12 5.6 510 0.14 0.09 E13 6.7 420 0.14 0.08

(84) TABLE-US-00018 TABLE 3 Structures of the materials used HIL1 0 HTL ETM1 LiQ H1 H2 H3 V-D1 V-D2 D3 D4 0 D5 D6 D7

(85) The results show that efficient OLEDs (external quantum efficiency) having a long lifetime (LT50) can be obtained with the compounds according to the invention, with deep-blue emission.

(86) By comparison, dopants V-D1 and V-D2 known from the prior art exhibit significantly worse values for the efficiency and the lifetime.