Substituted oxepines

Abstract

The invention relates to materials, to electroluminescence devices comprising said materials and to the use thereof.

Claims

1. A compound of the formula (10a) ##STR00459## wherein V is C(R.sup.4).sub.2; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sup.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by R.sup.2CR.sup.2, CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, CNR.sup.2, P(O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, or an aryloxy, arylalkoxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or a combination of two or more of these groups or a crosslinkable Q group; at the same time, two or more adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system which is optionally substituted by one or more R.sup.2 radicals; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.3).sub.2, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, C(O)R.sup.3, P(O)(R.sup.3).sub.2, S(O)R.sup.3, S(O).sub.2R.sup.3, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, CO, CS, CSe, CNR.sup.3, P(O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy, arylalkoxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.3 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.3 radicals, or a combination of two or more of these groups; at the same time, two or more adjacent R.sup.2 radicals together may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.3 is the same or different at each instance and is H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbyl radical having 1 to 40 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; at the same time, two or more R.sup.3 substituents together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system; R.sup.4 is as defined for R.sup.1, but the two R.sup.4 must not form a ring closure and with the proviso that at least one R.sup.1 is not H.

2. A process for preparing the compound as claimed in claim 1 with the aid of Suzuki coupling, Buchwald or Ullmann coupling.

3. A composition comprising at least one compound as claimed in claim 1 and at least one additional compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, hole blocker materials, n-dopants and p-dopants.

4. The composition as claimed in claim 3, wherein the additional compound is a phosphorescent emitter.

5. The composition as claimed in claim 3, wherein the additional compound is a host or matrix material.

6. The composition as claimed in claim 3, wherein the additional compound has a band gap of 2.5 eV or more.

7. A formulation comprising at least one compound as claimed in claim 1 and at least one solvent.

8. An electronic device comprising at least one compound as claimed in claim 1.

9. The electronic device as claimed in claim 8, wherein is selected from organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, organic photoreceptors.

10. The electronic device as claimed in claim 9, wherein the device is an organic electroluminescent device also selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs).

11. A process for producing the electronic device as claimed in claim 8, wherein at least one organic layer is applied by gas phase deposition or from solution.

12. A process for phototherapy of the skin which comprises treating the skin with the electronic device as claimed in claim 8.

13. A process for the reduction or prevention of skin ageing, skin wrinkles, crows' feet, acne, comedones and cellulite which comprises treating the skin with the electronic device according to claim 8.

14. A display or for lighting which comprises the electronic device as claimed in claim 8.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The reactants can be sourced from Aldrich (p-toluenesulfonic acid, N-bromosuccinimide, benzeneboronic acid, tri(o-tolyl)phosphine, potassium phosphate, palladium(II) acetate). 8,8-Dihydroxy-1,1-binaphthyl can be prepared by a literature method [J. Org. Chem., 1985, 50, 1486-1496]. The figures in square brackets for chemical compounds known from the literature are the CAS number.

Example 1

Synthesis of dinaphth[1,8-bc:1,8-ef]oxepine

(2) ##STR00149##

(3) To a boiling solution of 24.4 g of 8,8-dihydroxy-1,1-binaphthyl (85.2 mmol) in 500 mL of toluene are added, in small portions over the course of 2 h, 17.8 g (190 mmol) of p-toluenesulfonic acid. The mixture is then stirred for 1 h. After the reaction mixture has been cooled down, a solution of 25.9 g (187.5 mmol) of K.sub.2CO.sub.3 in 25 mL of water is added and the mixture is stirred for 1 h. The organic phase is removed, washed with 100 mL of water, dried with Mg.sub.2SO.sub.4 and then concentrated. Yield: 19.8 g (73.8 mmol), 87% of theory.

(4) In an analogous manner, it is possible to obtain the following compound:

(5) TABLE-US-00001 Reactant 1 Product Yield 0 49% [250716-74-6]

Example 2

Synthesis of 4,4-dibromodinaphth[1,8-bc:1,8-ef]oxepine

(6) ##STR00152##

(7) 19.6 g (73.0 mmol) of dinaphth[1,8-bc:1,8-ef]oxepine are dissolved in 200 mL of dimethylformamide, 27.3 g (178.0 mmol) of N-bromosuccinimide are added thereto and the reaction mixture is heated to 40 C. After 30 min, the mixture is allowed to cool and the precipitated yellow solid is filtered off and washed twice with 40 of ethanol. Yield: 31.1 g (63.4 mmol), 87% of theory; purity about 99% by .sup.1H NMR.

(8) In an analogous manner, it is possible to obtain the following compound:

(9) TABLE-US-00002 Reactant 1 Product Yield 78%

Example 3

Synthesis of 4-bromodinaphth[1,8-bc:1,8-ef]oxepine

(10) ##STR00155##

(11) 30 mg (0.11 mmol) of dinaphth[1,8-bc:1,8-ef]oxepine are dissolved in 5 mL of chloroform, 40 mg (0.22 mmol) of N-bromosuccinimide are added thereto and the reaction mixture is stirred at room temperature for 6 h. Thereafter, the reaction mixture is extended with 5 of dichloromethane, water is added and the organic phase is separated off. The column chromatography purification gives a yield of 25.3 mg (0.07 mmol, 65.2% of theory).

(12) In an analogous manner, it is possible to obtain the following compound:

(13) TABLE-US-00003 Reactant 1 Product Yield 78%

Example 4

Synthesis of dinaphth[1,8-bc:1,8-ef]oxepine-4-boronic acid

(14) ##STR00158##

(15) To a solution, cooled to 78 C., of 93.6 g (270 mmol) of 4-bromodinaphth[1,8-bc:1,8-ef]oxepine in 1500 mL of diethyl ether are added dropwise 110 mL (276 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred at 78 C. for 30 min. The mixture is allowed to come to room temperature and cooled again to 78 C., and then a mixture of 40 mL (351 mmol) of trimethyl borate in 50 mL of diethyl ether is added rapidly. After warming to 10 C., hydrolysis is effected with 135 mL of 2 N hydrochloric acid. The organic phase is removed, washed with water, dried over sodium sulfate and concentrated to dryness. The residue is taken up in 300 mL of n-heptane, and the colorless solid is filtered off with suction, washed with n-heptane and dried under reduced pressure. Yield: 77.6 g (248 mmol), 92% of theory.

(16) In an analogous manner, 0.5 eq. of bromide can be used to obtain the following compound:

(17) TABLE-US-00004 Reactant 1 Product Yield 0 78%

Example 5

Synthesis of 4,4-diphenyldinaphth[1,8-bc:1,8-ef]oxepine

(18) ##STR00161##

(19) 35 g (82.1 mmol) of 4,4-dibromodinaphth[1,8-bc:1,8-ef]oxepine, 22.0 g (180.7 mmol) of benzeneboronic acid and 38.3 g (180.7 mmol) of potassium phosphate are suspended in 500 mL of toluene, 250 mL of 1,4-dioxane and 120 mL of water. Added to the mixture are 1.3 g (4.1 mmol) of tri(o-tolyl)phosphine and then 461 mg (2 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 48 h. After cooling, the organic phase is removed, washed three times with 100 mL each time of water and concentrated. After purification by column chromatography (SiO.sub.2, n-heptane/dichloromethane 3:1), the foam obtained is dissolved in dichloromethane and precipitated with ethanol. The residue is recrystallized from toluene and from dichloromethane and finally sublimed under high vacuum (p=510.sup.5 mbar). Yield: 18.2 g (43.2 mmol), 53% of theory. Purity: about 99.9% by HPLC.

(20) In an analogous manner, it is possible to obtain the following compounds:

(21) TABLE-US-00005 Reactant 1 Reactant 2 Product Yield [128388-54-5] 59% [4688-76-0] 62% [13922-41-3] 0 71% [32316-92-0] 73% [13922-41-3] 69% 71% [854952-58-2] 0 65% [201802-67-7] 78% 69%

Example 6

Synthesis of 4 naphthalen-2-yldiphenyldinaphth[1,8-bc:1,8-ef]oxepine

(22) ##STR00189##

(23) 61 g (177 mmol) of 4-bromodinaphth[1,8-bc:1,8-ef]oxepine, 25.5 g (180.7 mmol) of 2-naphthylboronic acid and 38.3 g (180.7 mmol) of potassium phosphate are suspended in 500 mL of toluene, 250 mL of 1,4-dioxane and 120 mL of water. Added to the mixture are 1.3 g (4.1 mmol) of tri(o-tolyl)phosphine and then 461 mg (2 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 48 h. After cooling, the organic phase is removed, washed three times with 100 mL each time of water and concentrated. After purification by column chromatography (SiO.sub.2, n-heptane/dichloromethane 3:1), the foam obtained is dissolved in dichloromethane and precipitated with ethanol. The residue is recrystallized from toluene and from dichloromethane and finally sublimed under high vacuum (p=510.sup.5 mbar). Yield: 24 g (61.8 mmol), 59% of theory. Purity: about 99.9% by HPLC.

(24) In an analogous manner, it is possible to obtain the following compounds:

(25) TABLE-US-00006 Reactant 1 Reactant 2 Product Yield 0 [13922-41-3] 58% [1161009-88-6] 63% 62% [1001911-63-2] 00 [64377-31-1] 01 64% 02 03 04 59% 05 06 07 64% [201802-67-7] 08 09 0 75%

Example 7

Synthesis of 2,2-dibromo-4,4-diphenyldinaphth[1,8-bc:1,8-ef]oxepine

(26) ##STR00211##

(27) 2 g (4.8 mmol) of 4,4-diphenyldinaphth[1,8-bc:1,8-ef]oxepine are dissolved in 20 mL of dimethylformamide, 1.8 g (10.0 mmol) of N-bromosuccinimide are added thereto and the reaction mixture is heated to 80 C. After 1 h, the mixture is allowed to cool and the precipitated green solid is filtered off and washed with 5 mL each of cold DMF and water. Yield: 1.2 g (2.1 mmol), 44% of theory; purity about 96% by .sup.1H NMR.

Example 8

Synthesis of 2,2,4,4-tetraphenyldinaphth[1,8-bc:1,8-ef]oxepine

(28) ##STR00212##

(29) 5 g (8.6 mmol) of 4,4-dibromodinaphth[1,8-bc:1,8-ef]oxepine, 2.3 g (19.0 mmol) of benzeneboronic acid and 4.0 g (19.0 mmol) of potassium phosphate are suspended in 55 mL of toluene, 26 mL of 1,4-dioxane and 12.5 mL of water. Added to the mixture are 130 mg (0.43 mmol) of tri(o-tolyl)phosphine and then 48 mg (0.21 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 48 h. After cooling, the organic phase is removed, washed three times with 50 mL each time of water and concentrated. After column chromatography purification (SiO.sub.2, n-heptane/dichloromethane 3:1), the residue is recrystallized from toluene and from dichloromethane and then sublimed under high vacuum (p=510.sup.5 mbar). Yield: 3.2 g (5.6 mmol), 65% of theory. Purity: about 99.9% by HPLC.

(30) In an analogous manner, it is possible to obtain the following compounds:

(31) TABLE-US-00007 Reactant 1 Reactant 2 Product Yield 59% 76%

Example 9

Synthesis of N,N,N,N-tetrakis(biphenyl-4-yl)dinaphth[1,8-bc:1,8-ef]oxepine-4,4-diamine

(32) ##STR00219##

(33) A mixture of 12.3 g (50 mmol) of 4,4-dibromodinaphth[1,8-bc:1,8-ef]oxepine, 19.2 g (60 mmol) of bis(biphenyl-4-yl)amine, 7.7 g (80 mmol) of sodium tert-butoxide, 1.4 g (5 mmol) of tricyclohexylamine, 561 mg (2.5 mmol) of palladium(II) acetate and 300 mL of mesitylene is heated under reflux for 24 h. After cooling, 200 mL of water are added, the mixture is stirred for a further 30 min, the organic phase is removed and the latter is filtered through a short Celite bed and then the solvent is removed under reduced pressure. The residue is recrystallized five times from DMF and finally fractionally sublimed twice (p about 10.sup.6 mbar). Yield: 20.9 g (23 mmol), 80% of theory; purity: 99.9% by HPLC.

(34) In an analogous manner, it is possible to obtain the following compounds:

(35) TABLE-US-00008 Reactant 1 Reactant 2 0 Product Yield 63% 76% 75%

Example 10

Synthesis of 8-trimethylsilyltribenz[a,c,e]oxepine

(36) ##STR00229##

(37) 4.73 g (19.4 mmol) of tribenz[a,c,e]oxepine [2688-95-1] and 5.86 mL (4.57 g, 39.3 mmol, 2 mol %) of tetramethylethylenediamine (TMEDA) are dissolved in 60 mL of dry diethyl ether. Then 18.7 mL of n-butyllithium (2.5 M in hexane, 46.9 mmol, 2.4 mol %) are added and the reaction mixture is then heated to reflux for 2 h. Then the reaction mixture is cooled down 0 C., chlorotrimethylsilane (6.0 mL, 47.4 mmol) is added and the mixture is stirred overnight, in the course of which it is allowed to warm up to room temperature. 60 mL of water are added to the reaction mixture and the organic phase is separated off. The aqueous phase is extracted twice with 30 mL each time of diethyl ether and the combined organic phases are dried with MgSO.sub.4 and concentrated on a rotary evaporator. The oily crude product obtained is purified by column chromatography (SiO.sub.2, heptane) and gives 8-trimethylsilyltribenz[a,c,e]oxepine in 94% yield (5.76 g, 18.2 mmol) in the form of a colorless oil.

Example 11

Synthesis of tribenz[a,c,e]oxepine-1-boronic acid (Int-4)

(38) ##STR00230##

(39) To an initial charge of 9.82 g (31.03 mmol) of 8-trimethylsilyltribenz[a,c,e]oxepine in 50 mL of dry dichloromethane are then gradually added 37.2 mL of boron tribromide (1 M in dichloromethane (37.2 mmol, 1.2 mol %)). The reaction mixture is stirred for 15 h and then added to ice. The yellow organic phase is separated off, and the aqueous phase is extracted twice with 30 mL each time of ethyl acetate. The combined organic phases are washed with 30 mL each of water and saturated NaCl solution and then dried with Na.sub.2SO.sub.4, filtered and concentrated. The resultant yellow oil of Int-4 (8.4 g, 29.2 mmol, 94%) is converted further without further purification.

Example 12

Synthesis of 6-bromotribenz[a,c,e]oxepine (Int-5)

(40) ##STR00231##

(41) 10 g (41 mmol) of tribenz[a,c,e]oxepine are initially charged together with 8 mg of N-bromosuccinimide (45 mmol, 1.1 mol %) in 100 mL of dry dimethylformamide (DMF). The reaction mixture is heated to 120 C. for 24 h and then the solvent is removed under reduced pressure. The residue is purified by column chromatography on silica gel with heptane/DCM (2/1) as eluent. Int-5 is obtained as a pale yellowish solid in 76% yield (10 g, 31 mmol).

Example 13

Synthesis of 6,12-dibromotribenz[a,c,e]oxepine (Int-6)

(42) ##STR00232##

(43) 10 g (41 mmol) of tribenz[a,c,e]oxepine are initially charged together with 16 g of N-bromosuccinimide (90 mmol, 2.2 mol %) in 150 mL of dry dimethylformamide (DMF). The reaction mixture is heated to 120 C. for 24 h and then the solvent is removed under reduced pressure. The residue is purified by column chromatography on silica gel with heptane/DCM (2/1) as eluent. Int-6 is obtained as a yellow solid in 91% yield (15 g, 37 mmol).

Example 14

Synthesis of 2-(tribenz[a,c,e]oxepin-8-yl)-4,6-diphenyl-[1,3,5]triazine

(44) ##STR00233##

(45) 8.4 g (29.2 mmol) of tribenz[a,c,e]oxepine-1-boronic acid, 10.2 g of 2-chloro-4,6-diphenyl-[1,3,5]triazine (37.9 mmol, 1.3 mol %) and 6.8 g of Na.sub.2CO.sub.3 (64.1 mmol, 2.2 mol %) are initially charged in a mixture of 122 mL of toluene, 60 mL of 1,4-dioxane and 30 mL of water. Then 1.68 g of Pd(PPh.sub.3).sub.4 (1.46 mmol, 0.05 mol %) are added and the reaction mixture is heated to 80 C. for 15 h. The organic phase is separated off, extracted three times with 100 mL each time of water, dried with Na.sub.2SO.sub.4 and concentrated to dryness under reduced pressure. The crude product was purified by column chromatography (SiO.sub.2, heptane/CH.sub.2Cl.sub.2 2/1). The oxepine is obtained in 63% yield (8.74 g, 18.4 mmol) in the form of very fine pale yellowish crystals.

(46) In an analogous manner, it is possible to obtain the following compounds:

(47) TABLE-US-00009 Reactant 1 Reactant 2 0 0 0 Product Yield 78% 79% 88% 83% 0 84% 86% 82% 80% 85% 87% 82% 91% 90% 89% 0 93% 79%

(48) In an analogous manner, it is possible to obtain the following compounds with 0.5 eq. of corresponding boronic acid:

(49) TABLE-US-00010 Reactant 1 Reactant 2 Product Yield 79% 75% 0 76% 79%

Example 15

Synthesis of 3-(tribenz[a,c,e]oxepin-6-yl)-9-phenyl-9H-carbazole

(50) ##STR00294##

(51) 6-Bromotribenz[a,c,e]oxepine (Int-5) (132.3 mg; 0.41 mmol) and N-phenylcarbazole-3-boronic acid (129.3 mg; 0.45 mmol; 1.1 mol %) are initially charged together with potassium carbonate (124.5 mg; 0.90 mmol; 2.2 mol %) in a mixture of 3.5 mL of ethylene glycol dimethyl ether, 3.5 mL of toluene and 2.5 mL of demineralized water. Argon is passed through the mixture for 30 min. Added to the mixture thereafter are trio-tolyl)phosphine (3.37 mg; 0.011 mmol; 4 mol %) and Pd(OAc).sub.2 (1.24 mg; 0.006 mmol; 2 mol %). The reaction mixture is heated to 85 C. overnight. After cooling, the organic phase is separated off and the aqueous phase is extracted with 50 mL of CH.sub.2Cl.sub.2. The combined organic phases are extracted with 50 mL of water and dried with MgSO.sub.4. The solvent is removed under reduced pressure and the oily residue is purified by column chromatography on silica gel with heptane/DCM (2/1) as eluent. The target product is obtained as a pale yellowish solid in 72% yield (100.5 mg, 0.31 mmol).

(52) In an analogous manner, it is possible to obtain the following compounds:

(53) TABLE-US-00011 Reactant 1 Reactant 2 00 01 02 03 04 05 06 Product Yield 07 56% 08 92% 09 75% 0 76% 84% 89%

(54) In an analogous manner, it is possible to obtain the following compounds when 0.5 eq. of the boronic add is used:

(55) TABLE-US-00012 Reactant 1 Reactant 2 0 Product Yield 72% 74% 63% 72% 76%

Example 16

Synthesis of 2-(12-bromotribenz[a,c,e]oxepin-8-yl)-4,8-diphenyl-[1,3,5]triazine

(56) ##STR00328##

(57) 5 g (10.5 mmol) of 2-(tribenz[a,c,e]oxepin-8-yl)-4,6-diphenyl-[1,3,5]triazine are initially charged together with 2.06 g of N-bromosuccinimide (11.6 mmol, 110 mol %) in 100 mL of dry dimethylformamide (DMF). The reaction mixture is heated to 60 C. for 48 h and then the solvent is removed under reduced pressure. The residue is purified by column chromatography on silica gel with heptane/DCM (2/1) as eluent. The bromide is obtained as a colorless solid in 74% yield (431 g; 7.78 mmol).

(58) In an analogous manner, it is possible to obtain the following with 2 eq. of NBS corresponding dibromides:

(59) ##STR00329##

Example 17

Synthesis of 3-[10-(4,6-diphenyl-[1,3,5]triazine-2-yl)-tribenz[a,c,e]oxepin-6-yl]-9-phenyl-9H-carbazole

(60) ##STR00330##

(61) 5 g (9 mmol) of 2-(12-bromotribenz[a,c,e]oxepin-8-yl)-4,6-diphenyl-[1,3,5]triazine and N-phenylcarbazole-3-boronic acid (2.85 g; 9.9 mmol; 110 mol %) are initially charged together with potassium carbonate (2.74 g; 19.8 mmol; 220 mol %) in a mixture of 200 mL of ethylene glycol dimethyl ether, 200 mL of toluene and 150 mL of demineralized water. Argon is passed through the mixture for 30 min. Added to the mixture thereafter are trio-tolyl)phosphine (274 mg; 0.90 mmol; 10 mol %) and Pd(OAc).sub.2 (101 mg; 0.45 mmol; 5 mol %). The reaction mixture is heated to 85 C. overnight. After cooling, the organic phase is separated off and the aqueous phase is extracted with 50 mL of CH.sub.2Cl.sub.2. The combined organic phases are extracted with 50 mL of water and dried with MgSO.sub.4. The solvent is removed under reduced pressure and the oily residue is purified by column chromatography on silica gel with heptane/DCM (2/1) as eluent. The residue is recrystallized from toluene and finally sublimed under high vacuum (p=510.sup.6 mbar). Yield: 5.62 g (7.85 mmol), 87%; purity: 99.9% by HPLC.

(62) In an analogous manner, it is possible to obtain the following compounds:

(63) TABLE-US-00013 Reactant 1 Reactant 2 0 Product Yield 75% 69% 76% 79% 62%

Example 18

Synthesis of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9-oxatribenzo[a,c,e]cyclohepten-6-yl)-amine

(64) ##STR00346##

(65) A mixture of 16 g (50 mmol) of 6-bromotribenz[a,c,e]oxepine, 21.7 g (60 mmol) of 4-biphenyl-2-(9,9-dimethylfluorenyl)amine [897671-69-1], 7.7 g (80 mmol) of sodium tert-butoxide, 1.4 g (5 mmol) of tricyclohexylamine, 561 mg (2.5 mmol) of palladium(II) acetate and 300 mL of mesitylene is heated under reflux for 24 h. After cooling, 200 mL of water are added, the mixture is stirred for a further 30 min, the organic phase is removed and the latter is filtered through a short Celite bed and then the solvent is removed under reduced pressure. The residue is recrystallized five times from DMF and finally fractionally sublimed twice (p about 10.sup.6 mbar, T=330-340 C.). Yield: 21.7 g (34 mmol), 72%; purity: 99.9% by HPLC.

(66) In an analogous manner, it is possible to obtain the following compounds:

(67) TABLE-US-00014 Reactant 1 Reactant 2 0 0 Product Yield 43% 72% 61% 73% 67% 60% 64% 0 72%

(68) In an analogous manner, 0.5 eq. of dibromides can be used to obtain the following compounds:

(69) TABLE-US-00015 Reactant 1 Reactant 2 Product Yield 58% 69%

Example 19

Synthesis of 9-(9-oxatribenzo[a,c,e]cyclohepten-6-yl)-9-phenyl-9H,9H-[3,3]bicarbazolyl

(70) ##STR00377##

(71) 18.7 g (46 mmol) of 9-phenyl-3,3-bicarbazole and 14.8 g (46 mmol) of 6-bromotribenz[a,c,e]oxepine are dissolved in 450 mL of toluene and degassed by means of introduction of protective gas. This is followed by addition of 7 mL (7 mmol, 1 M solution in toluene) of tri-tert-butylphosphine, 633.8 mg (2.82 mmol) of Pd(OAc).sub.2 and 7 g (76 mmol) of NaOtBu. The solids are degassed beforehand, and the reaction mixture is post-degassed and then stirred under reflux for 3 h. The warm reaction solution is filtered through Alox B (activity level 1), washed with water, dried and concentrated. The residue is recrystallized from toluene and finally sublimed under high vacuum (p=510.sup.6 mbar). Yield: 24 g (38 mmol), 83%; purity: 99.9% by HPLC.

(72) In an analogous manner, it is possible to obtain the following compounds:

(73) TABLE-US-00016 Reactant 1 Reactant 2 0 Product Yield 68% 65% 64% 61%

(74) In an analogous manner, 0.5 eq. of the corresponding dibromides can be used to obtain the following compound:

(75) TABLE-US-00017 Reactant 1 Reactant 2 Product Yield 0 68%

Example 20

Synthesis of (2-chlorophenyl)-(9-oxatribenzo[a,c,e]cyclohepten-6-yl)amine

(76) ##STR00393##

(77) 25.5 g (79 mmol) of 6-bromotribenz[a,c,e]oxepine, 10 mL (95 mmol) of 2-chloroaniline, 36.3 g (111 mmol) of cesium carbonate, 0.89 g (3.9 mmol) of palladium(II) acetate and 3.9 g (6 mmol) of 2,2-bis(diphenylphosphanyl)-[1,1]binaphthalene are dissolved in 500 mL of toluene and stirred under reflux for 5 h. The reaction mixture is cooled down to room temperature, extended with toluene and filtered through Celite. The filtrate is concentrated under reduced pressure and the residue is crystallized from toluene/heptane. The product is isolated as a colorless solid. Yield: 22 g (61 mmol), 78% of theory.

Example 21

(78) Cyclization

(79) ##STR00394##

(80) 36.7 g (102 mmol) of (2-chlorophenyl)-(9-oxatribenzo[a,c,e]cyclohepten-6-yl)-amine, 32 g (268 mmol) of potassium carbonate, 0.6 g (2.7 mmol) of palladium(II) acetate and 4.2 mL (4.2 mmol) of tri-tert-butylphosphine are suspended in 350 mL of dimethylacetamide and stirred under reflux for 6 h. After the reaction mixture has cooled, 300 mL of water and 400 mL of ethyl acetate are added. The mixture is stirred for a further 30 min, the organic phase is separated off and filtered through a short Celite bed, and then the solvent is removed under reduced pressure. The crude product is subjected to hot extraction with toluene and recrystallized from toluene. The isomers are separated by chromatography. Yield: 30 g (91 mmol), 92% of theory.

Example 22

(81) Acylation

(82) ##STR00395##

(83) 35 g (106 mmol) of compound 21a, 17.9 g (114 mmol) of bromobenzene and 30.5 g of NaOtBu are suspended in 1.5 L of p-xylene. To this suspension are added 0.5 g (2.11 mmol) of Pd(OAc).sub.2 and 6 mL of a 1M tri-tert-butylphosphine (1 M solution in toluene). The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, washed three times with 200 mL each time of water and then concentrated to dryness. The residue is hot-extracted with toluene, recrystallized from toluene and finally sublimed under high vacuum; purity is 99.9% at a yield of 29 g (73 mmol; 69%).

(84) In an analogous manner, it is possible to prepare the following compound:

(85) TABLE-US-00018 Reactant 1 Reactant 2 00 01 02 03 Product Yield 04 78% 05 79% 06 88% 07 83%

Example 23

(86) Production of OLEDs

(87) OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 04/058911, which is adapted to the circumstances described here (variation in layer thickness, materials).

(88) In the examples which follow (see tables 1 and 2), the data of various OLEDs are presented. Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm.

(89) The OLEDs basically have the following layer structure: substrate/interlayer (IL)/hole injection layer (HIL)/electron blocker layer (EBL)/emission layer (EML)/electron transport layer (ETL)/electron injection layer (EIL) and finally a cathode. The EIL is obtained by vapor deposition of a 2 nm-thick layer consisting of Liq. The cathode is formed by an aluminum layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 1. The materials required for production of the OLEDs are shown in Table 3.

(90) All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as H1:D1 (95%:5%) mean here that the material H1 is present in the layer in a proportion by volume of 95% and SEB1 in a proportion of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(91) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IDL characteristics) assuming Lambertian radiation characteristics, and also the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. The parameter EQE @ 1000 cd/m.sup.2 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2. LD80 @ 100 mA/cm.sup.2 or 60 mA/cm.sup.2 is the lifetime by which the OLED has dropped to 80% of the starting intensity when the OLED is being operated at a current of 100 mA/cm.sup.2 or 60 mA/cm.sup.2. For green-emitting OLEDs a starting brightness of 100 mA/cm.sup.2 is chosen, and for blue-emitting OLEDs a starting brightness of 60 mA/cm.sup.2. The data for the various OLEDs are collated in Table 2.

(92) Use of Inventive Compounds as Matrix Materials, as Emitter and as Electron Transport Material in Green- or Blue-Fluorescing OLEDs

(93) The inventive compounds are especially suitable as matrix material, dopant or else as electron transport material in OLEDs. They are suitable as an individual layer, but also as a mixed component within the EML or ETL. Compared to reference components (C1 or C4), all samples comprising the inventive compounds exhibit higher efficiencies, lower operating voltage and/or distinctly improved lifetimes in green- or blue- or green-fluorescing OLEDs, Component C5 comprising the inventive compound INV-3 exhibits a much deeper color than the reference component C4.

(94) TABLE-US-00019 TABLE 1 Structure of the OLEDs IL HIL EBL Thickness/ Thickness/ Thickness/ EML ETL Ex. nm nm nm Thickness/nm Thickness/nm C1 HIL1 HIL2 NPB H1(95%):G1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 20 nm 20 nm 30 nm C2 HIL1 HIL2 NPB INV-1(95%):G1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 20 nm 20 nm 30 nm C3 HIL1 HIL2 NPB INV-2(95%):G1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 20 nm 20 nm 30 nm C4 HIL1 HIL2 NPB H1(95%):B1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 20 nm 20 nm 30 nm C5 HIL1 HIL2 NPB H1(95%):INV-3(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 20 nm 20 nm 30 nm C6 HIL1 HIL2 NPB H1(95%):B1(5%) INV-6(50%):LiQ(50%) 5 nm 140 nm 20 nm 20 nm 30 nm

(95) TABLE-US-00020 TABLE 2 Data of the OLEDs LD80 @ 100 mA/cm.sup.2 EQE or @ 1000 cd/m2 U @ 1000 cd/m2 60 mA/cm.sup.2 CIE Ex. % V [h] x y C1 7.0 4.2 190 0.27 0.66 C2 7.5 4.4 190 0.27 0.67 C3 6.8 4.0 270 0.27 0.67 C4 6.3 5.0 210 0.14 0.16 C5 6.7 4.7 200 0.13 0.14 C6 6.3 4.8 250 0.14 0.16

(96) TABLE-US-00021 TABLE 3 Materials used 08 HIL1 09 HIL2 0 NPB H1 LiQ ETM1 G1 B1 INV-1 INV-2 INV-3 INV-4

Example 24

(97) Production of OLEDs

(98) In examples I1 to I27 which follow (tables 4 and 5), the data of various OLEDs are presented. Cleaned glass plates (cleaning in laboratory washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm, for improved processing, are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and baked at 180 C. for 10 min. These coated glass plates form the substrates to which the OLEDs are applied.

(99) The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/interlayer (IL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 4. A designation such as INV-10 in the table relates to the inventive materials, the structure of which is shown in table 6.

(100) All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as IC1:INV-7:TEG2 (59%:29%:12%) mean here that the material IC1 is present in the layer in a proportion by volume of 59%, INV-7 in a proportion of 29% and TEG2 in a proportion of 12%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(101) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. The parameter U1000 in Table 5 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2. The data for the various OLEDs are collated in Table 5. It is observed that excellent performance data can be achieved with inventive materials when they are used as hole transport material, as matrix material for phosphorescent emitters, and when they are used as electron transport material.

(102) TABLE-US-00022 TABLE 4 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness I1 HATCN SpMA1 SpMA2 INV-5:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (83%:17%) 30 nm 10 nm (50%:50%) 30 nm I2 HATCN SpMA1 SpMA2 IC1:INV-6:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (44%:44%:12%) 30 nm 10 nm (50%:50%) 30 nm I3 HATCN SpMA1 SpMA2 IC1:INV-7:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (59%:29%:12%) 30 nm 10 nm (50%:50%) 30 nm I4 HATCN SpMA1 SpMA2 INV-5:INV-8:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (44%:44%:12%) 30 nm 10 nm (50%:50%) 30 nm I5 HATCN SpMA1 SpMA2 IC3:INV-9:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (55%:35%:10%) 30 nm 10 nm (50%:50%) 30 nm I6 HATCN SpMA1 INV-10 IC3:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (83%:17%) 30 nm 10 nm (50%:50%) 30 nm I7 HATCN SpMA1 INV-11:TEG1 ST2 ST2:LiQ 5 nm 60 nm (83%:17%) 30 nm 10 nm (50%:50%) 30 nm I8 HATCN SpMA1 SpMA2 ST1:INV-12:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (28%:55%:17%) 30 nm 10 nm (50%:50%) 30 nm I9 HATCN SpMA1 SpMA2 L1:INV-13:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (33%:50%:17%) 30 nm 10 nm (50%:50%) 30 nm I10 HATCN SpMA1 SpMA2 IC1:INV-14:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (44%:44%:12%) 30 nm 10 nm (50%:50%) 30 nm I11 HATCN SpMA1 SpMA2 L2:INV-15:TEG2 ST2:LiQ 5 nm 50 nm 10 nm (42%:41%:17%) 30 nm (50%:50%) 40 nm I12 HATCN SpMA1 SpMA2 IC1:INV-16:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (44%:44%:12%) 30 nm 10 nm (50%:50%) 30 nm I13 HATCN SpMA1 SpMA2 IC1:TEG2 ST2 INV-17 LiQ 5 nm 50 nm 10 nm (83%:17%) 30 nm 10 nm 30 nm 3 nm I14 HATCN SpMA1 SpMA2 IC1:INV-18:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (44%:44%:12%) 30 nm 10 nm (50%:50%) 30 nm I15 HATCN SpMA1 SpMA2 INV-19:TEG2 ST2:LiQ 5 nm 50 nm 10 nm (83%:17%) 30 nm (50%:50%) 40 nm I16 HATCN SpMA1 SpMA2 INV-20:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (83%:17%) 30 nm 10 nm (50%:50%) 30 nm I17 HATCN SpMA1 SpMA2 IC1:TEG2 ST2 INV-20:LiQ 5 nm 50 nm 10 nm (83%:17%) 30 nm 10 nm (50%:50%) 30 nm I18 SpA1 HATCN SpMA1 9a:IC2:TER3 IC3 ST2:LiQ 90 nm 5 nm 130 nm (40%:50%:10%) 40 nm 5 nm (50%:50%) 35 nm I19 HATCN SpMA1 INV-21 IC3:TEG1 ST2 ST2:LiQ 5 nm 50 nm 10 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I20 HATCN SpMA1 INV-22 IC1:TEG2 ST2 ST2:LiQ 5 nm f50 nm 10 nm (83%:17%) 30 nm 10 nm (50%:50%) 30 nm I21 HATCN SpMA1 INV-23 IC1:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (83%:17%) 30 nm 10 nm (50%:50%) 30 nm I22 HATCN INV-24 SpMA1 IC3:TEG1 IC3 ST2:LiQ 5 nm 50 nm 10 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I23 HATCN SpMA1 SpMA2 L1:INV-25:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (29%:59%:12%) 30 nm 10 nm (50%:50%) 30 nm I24 HATCN SpMA1 SpMA2 L1:INV-26:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (29%:59%:12%) 30 nm 10 nm (50%:50%) 30 nm I25 HATCN SpMA1 SpMA2 IC1:INV-27:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (44%:44%:12%) 30 nm 10 nm (50%:50%) 30 nm I26 HATCN SpMA1 SpMA2 IC1:INV-28:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (40%:48%:12%) 30 nm 10 nm (50%:50%) 30 nm I27 HATCN SpMA1 SpMA2 INV-29:TEG2 ST2 ST2:LiQ 5 nm 50 nm 10 nm (83%:17%) 30 nm 10 nm (50%:50%) 30 nm

(103) TABLE-US-00023 TABLE 5 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 I1 3.4 62 58 16.6% 0.34/0.62 I2 3.2 67 70 18.1% 0.34/0.62 I3 3.4 57 52 15.4% 0.34/0.62 I4 3.4 68 63 18.4% 0.34/0.62 I5 3.2 75 73 20.2% 0.34/0.62 I6 3.2 76 75 20.7% 0.34/0.62 I7 3.5 74 67 20.0% 0.33/0.63 I8 3.3 68 64 18.3% 0.34/0.62 I9 3.1 72 72 19.5% 0.34/0.62 I10 3.3 62 59 16.8% 0.34/0.62 I11 3.1 72 73 19.4% 0.33/0.63 I12 3.2 72 71 19.3% 0.34/0.62 I13 3.5 65 59 17.5% 0.35/0.62 I14 3.2 68 68 18.6% 0.35/0.62 I15 3.1 77 79 20.8% 0.34/0.62 I16 3.8 62 52 16.7% 0.33/0.63 I17 4.4 65 47 17.7% 0.35/0.62 I18 4.6 11.2 8.2 12.2% 0.67/0.33 I19 3.3 72 69 19.8% 0.36/0.61 I20 3.2 62 62 17.0% 0.35/0.61 I21 3.2 64 63 17.3% 0.35/0.62 I22 3.4 73 67 20.0% 0.34/0.62 I23 3.3 59 56 16.0% 0.35/0.61 I24 3.2 61 60 16.7% 0.35/0.62 I25 3.2 71 70 19.1% 0.33/0.63 I26 3.5 63 58 17.2% 0.36/0.61 I27 4.1 72 55 19.4% 0.35/0.62

(104) TABLE-US-00024 TABLE 6 Structural formulae of the materials for the OLEDs 0 SpA1 TEG1 SpMA1 SpMA2 TEG2 HATCN ST2 ST1 IC1 IC2 0 L1 L2 IC3 TER3 INV-5 INV-6 INV-7 INV-8 INV-9 INV-10 0 INV-11 INV-12 INV-13 INV-14 INV-15 INV-16 INV-17 INV-18 INV-19 INV-20 0 INV-21 INV-22 INV-23 INV-24 INV-25 INV-26 INV-27 INV-28 INV-29