HETEROCYCLIC COMPOUNDS WITH BENZO(C)COUMARIN-STRUCTURES

Abstract

The invention relates to heterocyclic compounds with benzo[c]coumarin structures and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Claims

1.-25. (canceled)

26. A compound comprising structures of the formula (I) ##STR00552## where the symbols used are as follows: R is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar.sup.1, S(═O).sub.2Ar.sup.1, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by C≡C, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.2), SO, SO.sub.2, O, S or CONR.sup.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more adjacent R substituents may also form a mono- or polycyclic aliphatic or aromatic ring system with one another, with the ring to which R is bonded, with a ring to which R is adjacent or with an R.sup.1 radical; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar, S(═O).sub.2Ar.sup.1, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.2), SO, SO.sub.2, O, S or CONR.sup.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.1 substituents may also form a mono- or polycyclic aliphatic or aromatic ring system with one another, with the ring to which R.sup.1 is bonded, with a ring to which R.sup.1 is adjacent or with an R radical; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar.sup.1, S(═O).sub.2Ar.sup.1, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by C≡C, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.3), SO, SO.sub.2, O, S or CONR.sup.3 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.2 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, it is also possible for two Ar.sup.1 radicals bonded to the same phosphorus atom to be joined to one another by a single bond or a bridge selected from B(R.sup.3), C(R.sup.3).sub.2, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, C≡C(R.sup.3).sub.2, O, S, S═O, SO.sub.2, N(R.sup.3), P(R.sup.3) and P(═O)R.sup.3; 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 20 carbon atoms, in which hydrogen atoms may also be replaced by F; at the same time, two or more adjacent R.sup.3 substituents may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; m, n are each independently 0, 1, 2, 3 or 4; with the proviso that the sum of m and n is not less than 1; at least one of the R and/or R.sup.1 groups in formula (I) is at least one L group; and L is an aromatic group having 10 to 40 carbon atoms or a heteroaromatic group having 6 to 40 carbon atoms, where the aromatic and/or heteroaromatic group comprises at least two adjacent aromatic and/or heteroaromatic rings, each of which may be fused or unfused and/or may be substituted by one or more R.sup.2 radicals.

27. The compound as claimed in claim 26, wherein the sum total of the indices m and n is not more than 3.

28. The compound as claimed in claim 26, wherein the structure of formula (I) has one or two L groups.

29. The compound as claimed in claim 26, wherein the L group in formula (I) comprises at least three aromatic or heteroaromatic rings which may be unfused or fused.

30. The compound as claimed in claim 26, wherein the L group in formula (I) comprises at least one biphenyl, fluorenyl and/or spirobifluorenyl group.

31. The compound as claimed in claim 26, wherein the index m is 1 or 2 and at least one of the R radicals is an L group, where the index n is 0.

32. The compound as claimed in claim 26, wherein the index n is 1 or 2 and at least one of the R.sup.1 radicals is an L group, where the index m is 0.

33. The compound as claimed in claim 26, wherein the index m is 1 or 2 and the index n is 1 or 2, where at least one of the R radicals is an L group and at least one of the R.sup.1 radicals is an L group.

34. The compound as claimed claim 26, wherein, in the structure of formula (I), at least one L radical is a group selected from the formulae (L-1) to (L-14) ##STR00553## ##STR00554## where the dotted bond marks the attachment position, g is 0, 1, 2, 3, 4 or 5, h is 0, 1, 2, 3 or 4, j is 0, 1, 2 or 3, Y is O, S or N(R.sup.1), and R.sup.1 and R.sup.2 have the definition given in claim 26.

35. The compound as claimed in claim 26, wherein the L group in formula (I) comprises at least one heteroaryl group having a nitrogen atom.

36. The compound as claimed in claim 26, wherein the L group in formula (I) comprises at least one carbazole, diazine, triazine, benzothiophene and/or benzofuran group.

37. The compound as claimed in claim 26, wherein, in the structure of formula (I), at least one L radical is a group selected from the formulae (L-15) to (L-39) ##STR00555## ##STR00556## ##STR00557## ##STR00558## ##STR00559## where the dotted bond marks the attachment position, g is 0, 1, 2, 3, 4 or 5, h is 0, 1, 2, 3 or 4, j is 0, 1, 2 or 3, k is 0, 1 or 2, Y is O, S or N(R′), and R.sup.1 and R.sup.2 have the definition given in claim 26.

38. The compound as claimed in claim 26, wherein, in the structure of formula (I), at least one L radical is a group selected from the formulae (L-40) to (L-42) ##STR00560## here the dotted bond marks the attachment position and Ar.sup.2, Ar.sup.3, Ar.sup.4 are each independently an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals; p is 0 or 1 and X is a bond, CR.sup.1.sub.2, C═O, N(R.sup.1), B(R.sup.1), SiR.sup.1.sub.2, O or S, where the R.sup.1 and Ar.sup.1 radicals have the definition given in claim 26.

39. The compound as claimed claim 26, wherein the structure of formula (I) comprises not more than one reactive group.

40. The compound as claimed in claim 39, wherein the structure of formula (I) has at most the reactive group selected from Br, Cl and B(OR.sup.2).sub.2.

41. The compound as claimed in claim 26, wherein the compound comprises structures of the formulae (II), (III), (IV), (V), (VI), (VII), (VIII) and/or (IX) ##STR00561## ##STR00562## where the symbols R, R.sup.1, L shown and the indices m and n have the definition detailed in claim 26, and the index j is 0, 1, 2 or 3 and R.sup.4 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar.sup.1, S(═O).sub.2Ar.sup.1, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.2), SO, SO.sub.2, O, S or CONR.sup.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, where the R.sup.2 and Ar.sup.1 radicals have the definition given in claim 26, or a combination of these systems; at the same time, two or more adjacent R.sup.4 substituents may also form a mono- or polycyclic aliphatic or aromatic ring system with one another, with the ring to which R.sup.4 is bonded, with a ring to which R.sup.4 is adjacent or with an R or R.sup.1 radical.

42. The compounds as claimed in claim 26, wherein the compound comprises structures of the formulae (X), (XI), (XII), (XIII), (XIV), (XV), (XVI) and/or (XVII) ##STR00563## ##STR00564## where the symbols R, R.sup.1, L shown and the indices m and n have the definition detailed in claim 26, and the index j is the same or different at each instance and is 0, 1, 2 or 3 and R.sup.4 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(═O)Ar.sup.1, P(═O)(Ar.sup.1).sub.2, S(═O)Ar.sup.1, S(═O).sub.2Ar.sup.1, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.2), SO, SO.sub.2, O, S or CONR.sup.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, where the R.sup.2 and Ar.sup.1 radicals have the definition given in claim 26, or a combination of these systems; at the same time, two or more adjacent R.sup.4 substituents may also form a mono- or polycyclic aliphatic or aromatic ring system with one another, with the ring to which R.sup.4 is bonded or with a ring to which R.sup.4 is adjacent.

43. The compound as claimed in claim 41, wherein the R.sup.4 radical is not an aromatic group having 10 to 40 carbon atoms or a heteroaromatic group having 6 to 40 carbon atoms, where the aromatic and/or heteroaromatic group comprises at least two adjacent aromatic and/or heteroaromatic rings, each of which may be fused or unfused and/or may be substituted by one or more R.sup.2 radicals.

44. The compound as claimed in claim 26, wherein the compound has a molecular weight of not more than 5000 g/mol.

45. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 26, wherein one or more bonds of the compound to the polymer, oligomer or dendrimer are present.

46. A composition comprising at least one compound as claimed in claim 26 and/or an oligomer, polymer or dendrimer as claimed in claim 45 and at least one further 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 and hole blocker materials.

47. A formulation comprising at least one compound as claimed in claim 26, an oligomer, polymer or dendrimer as claimed in claim 45 and/or at least one composition as claimed in claim 46 and at least one solvent.

48. A process for preparing a compound as claimed in claim 26 or an oligomer, polymer or dendrimer as claimed in claim 45, comprising joining a coumarin compound to an aryl and/or heteroaryl group via a coupling reaction.

49. A method comprising utilizing of a compound as claimed in claim 26, of an oligomer, polymer or dendrimer as claimed in claim 45, or of a composition as claimed in claim 46 in an electronic device as hole transport material, hole injection material, hole blocker material, electron injection material, electron blocker material and/or electron transport material.

50. An electronic device comprising at least one compound as claimed in claim 26, an oligomer, polymer or dendrimer as claimed in claim 45, or a composition as claimed in claim 46, wherein the electronic device is preferably selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells and organic laser diodes.

Description

EXAMPLES

[0153] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

Preparation Examples

a) 1-Bromodibenzofuran

[0154] ##STR00254##

[0155] 111 g (416 mmol) of 6′-bromo-2′-fluorobiphenyl-2-ol are dissolved in 2 L of DMF (max. 0.003% H.sub.2O) SeccoSolv® and cooled to 5° C. 20 g (449 mmol) of sodium hydride (60% suspension in paraffin oil) are added to this solution in portions and, once the addition has ended, the mixture is stirred for 20 min, and then the mixture is heated to 100° C. for 45 min. After the cooling, 500 mL of ethanol are added gradually to the mixture, which is completely concentrated by rotary evaporation and then purified by chromatography. Yield: 90 g (367 mmol), 88.5% of theory.

[0156] The following compounds are prepared in an analogous manner:

TABLE-US-00002 Reactant 1 Product Yield a1 [00255] [00256] 73% a2 [00257] [00258] 79%

b) Dibenzofuran-1-boronic acid

[0157] ##STR00259##

[0158] 180 g (728 mmol) of 1-bromodibenzofuran are dissolved in 1500 mL of dry THF and cooled to 78° C. At this temperature, 305 mL (764 mmol/2.5 M in hexane) of n-BuLi are added within about 5 min, and then the mixture is stirred at −78° C. for a further 2.5 h. At this temperature, 151 g (1456 mmol) of trimethyl borate are added very rapidly and the reaction is allowed to come gradually to RT (about 18 h). The reaction solution is washed with water and the precipitated solids and the organic phase are subjected to azeotropic drying with toluene. The crude product is extracted while stirring from toluene/methylene chloride at about 40° C. and filtered off with suction. Yield: 146 g (690 mmol), 95% of theory.

[0159] The following compounds are prepared in an analogous manner:

TABLE-US-00003 Reactant 1 Product Yield b1 [00260] [00261] 73% b2 [00262] [00263] 79% b3 [00264] [00265] 73%

c) Synthesis of 5″-chloro-[1,3′;1′,1″;3″,1′″;3′″,1″″]quinquephenyl

[0160] ##STR00266##

[0161] 29 g (148 mmol) of 3-biphenylboronic acid, 20 g (74 mmol) of 1-chloro-3,5-dibromobenzene and 60 g (596 mmol) of sodium carbonate are suspended in 500 mL of THF and 300 mL of water. 6.5 g (5.6 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene. The yield is 22 g (53 mmol), corresponding to 71% of theory.

[0162] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00004 Example Reactant 1 Reactant 2 Product Yield c1 [00267] [00268] [00269] 95% c2 [00270] [00271] [00272] 73% c3 [00273] [00274] [00275] 83%

d) Synthesis of 4,4,5,5-tetramethyl-2-[1,3′;1′,1″3″,1′″;3′″,1″″]quinquephenyl-5″-yl-[1,3,2]dioxaborolane

[0163] ##STR00276##

[0164] 75 g (126 mmol) of 5″-chloro-[1,3′;1′,1″;3″,1′″;3′″,1″″]quinquephenyl, 41.6 g of bis(pinacolato)diborane (163 mmol), 21 g (214 mmol) of potassium acetate and 18 g (25 mmol) of tricyclohexylphosphinepalladium dichloride are heated to reflux in 1 L of 1,4-dioxane while stirring vigorously for 2 days. The reaction mixture is filtered through Celite at room temperature. The solvent is removed under reduced pressure, and the remaining solids are recrystallized in acetonitrile. The solids formed are filtered off and washed with heptane. The yield is 82 g (119 mmol), corresponding to 95% of theory.

[0165] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00005 Example Reactant 1 Product Yield d1 [00277] [00278] 90% d2 [00279] [00280] 84% d3 [00281] [00282] 75%

e) Synthesis of 8-bromodibenzo[b,d]pyran-6-one

[0166] ##STR00283##

[0167] 100 g (386 mmol) of 2-bromofluorenone are initially charged in 1000 mL of trifluoroacetic acid and cooled to 0° C. Added gradually to this solution are 100 g (637 mmol) of sodium percarbonate (13%-14% active oxygen), and the reaction mixture is stirred at 10-15° C. for 1 h. Subsequently, stirring of the mixture continues at room temperature overnight. 1000 mL of water are added to the reaction mixture, and the organic phase is removed and then concentrated to dryness. The residue is triturated with heptane, filtered off with suction and dried at 50° C. under reduced pressure.

[0168] Yield: 92 g (334 mmol), 86% of theory.

[0169] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00006 Example Reactant 1 Product Yield e1 [00284] [00285] 50% e2 [00286] [00287] 63% e3 [00288] [00289] 61%

f) 8-(9-Phenyl-9H-carbazol-3-yl)benzo[c]chromen-6-one

[0170] ##STR00290##

[0171] 17 g (67 mmol) of 9-phenyl-9H-carbazole-3-boronic acid, 22.2 g (81 mmol) of 8-bromo-6H-dibenzo[b,d]pyran-6-one and 136 g (980 mmol) of tripotassium phosphate are suspended in 1000 mL of THF and 300 mL of water. Added to this suspension are 178 mg (0.67 mmol) of triphenylphosphine and then 152 mg (0.67 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene/heptane and finally sublimed under high vacuum (p=5×10.sup.−5 mbar, T=377° C.). The yield is 23 g (54 mmol), corresponding to 82% of theory.

[0172] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield f1 [00291] [00292] [00293] 78% f2 [00294] [00295] [00296] 70% f3 [00297] [00298] [00299] 75% f4 [00300] [00301] [00302] 77% f5 [00303] [00304] [00305] 75% f6 [00306] [00307] [00308] 62% f7 [00309] [00310] [00311] 83% f8 [00312] [00313] [00314] 84% f9 [00315] [00316] [00317] 79% f10 [00318] [00319] [00320] 83% f11 [00321] [00322] [00323] 75% f12 [00324] [00325] [00326] 77% f13 [00327] [00328] [00329] 74% f14 [00330] [00331] [00332] 69% f15 [00333] [00334] [00335] 68% f16 [00336] [00337] [00338] 80% f17 [00339] [00340] [00341] 71% f18 [00342] [00343] [00344] 69% f19 [00345] [00346] [00347] 71% f20 [00348] [00349] [00350] 71%

[0173] In an analogous manner, it is possible to prepare the following compound with 0.5 eq. of boronic acid or bromide.

TABLE-US-00008 Reactant 1 Reactant 2 Product Yield f21 [00351] [00352] [00353] 74% f22 [00354] [00355] [00356] 76% f23 [00357] [00358] [00359] 70% f24 [00360] [00361] [00362] 72%

g) 3-Hydroxy-8-methoxybenzo[c]chromen-6-one

[0174] ##STR00363##

[0175] 83 g (343 mmol) of sodium hydroxide are dissolved in 1000 mL of water. 80 g (346 mmol) of 2-bromo-5-methoxybenzoic acid and 76.5 g (695 mmol) of benzene-1,3-diol are added and the mixture is boiled under reflux for 30 min. Added to this suspension is a solution of 7 g (28 mmol) of copper sulfate pentahydrate dissolved in 300 mL of water, and the reaction mixture is heated under reflux for 1 h. After cooling, the solids are filtered off, mixed washed once with 200 mL of heptane and then concentrated to dryness. The yield is 50 g (165 mmol), corresponding to 80% of theory.

[0176] In an analogous manner, it is possible to obtain the following compounds,

TABLE-US-00009 Reactant 1 Reactant 2 Product Yield g1 [00364] [00365] [00366] 80% g2 [00367] [00368] [00369] 87% g3 [00370] [00371] [00372] 85%

h) 8-Methoxy-6-oxo-6H-benzo[c]chromen-3-yl trifluoromethanesulfonate

[0177] ##STR00373##

[0178] 83 g (343 mmol) of 3-hydroxy-8-methoxybenzo[c]chromen-6-one are suspended in 1200 mL of dichloromethane at 0° C. 37 mL (267 mmol) of triethylamine, 57 mL (343 mmol) of trifluoromethanesulfonate in 250 mL of dichloromethane, in such a way that the temperature does not rise above 5° C. The mixture is stirred at 0° C. for a further 1 h, then stirring is continued at room temperature overnight. The solids are filtered off, mixed washed once with 200 mL of water/MeOH and then concentrated to dryness. The yield is 102 g (275 mmol), corresponding to 80% of theory.

[0179] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00010 Reactant 1 Product Yield h1 [00374] [00375] 81% h2 [00376] [00377] 82% h3 [00378] [00379] 79%

j) 8-Methoxy-3-(9-phenyl-9H-carbazol-3-yl)benzo[c]chromen-6-one

[0180] ##STR00380##

[0181] 27 g (72 mmol) of 8-methoxy-6-oxo-6H-benzo[c]chromen-3-yl trifluoromethanesulfonate, 31 g (108 mmol) of (9-phenylcarbazol-3-yl)boronic acid and 8.3 g (7.2 mmol) of tetrakis(triphenylphosphine)palladium(0) and 25 mL (180 mmol) of triethylamine are suspended in 700 mL of 1,2-dimethoxyethane and the reaction mixture is heated under reflux at 110° C. for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene/heptane. The yield is 20 g (42 mmol), corresponding to 60% of theory.

[0182] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00011 Reactant 1 Reactant 2 Product Yield j1 [00381] [00382] [00383] 63% j2 [00384] [00385] [00386] 68% j3 [00387] [00388] [00389] 72% j4 [00390] [00391] [00392] 75% j5 [00393] [00394] [00395] 70% j6 [00396] [00397] [00398] 76% j7 [00399] [00400] [00401] 81% j8 [00402] [00403] [00404] 82% j9 [00405] [00406] [00407] 79% j10 [00408] [00409] [00410] 78%

i) 8-Hydroxy-3-(9-phenyl-9H-carbazol-3-yl)benzo[c]chromen-6-one

[0183] ##STR00411##

[0184] 83 g (178 mmol) of 8-methoxy-3-(9-phenyl-9H-carbazol-3-yl)benzo[c]-chromen-6-one and 1500 mL of dichloromethane are cooled to 0° C., 100 mL (1054 mmol) of tribromoborane are added gradually and the mixture is stirred at room temperature for 16 h. Thereafter, hydrolysis is effected with 100 mL of methanol and the solids are filtered off with suction. The residue is recrystallized from heptane. The yield is 46 g (103 mmol), corresponding to 57% of theory.

[0185] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00012 Reactant 1 Product Yield i1 [00412] [00413] 65% i2 [00414] [00415] 64% i3 [00416] [00417] 70% i4 [00418] [00419] 65% i5 [00420] [00421] 60% i6 [00422] [00423] 71% i7 [00424] [00425] 69% i8 [00426] [00427] 78% i9 [00428] [00429] 73% i10 [00430] [00431] 67%

k) 6-Oxo-3-(9-phenyl-9H-carbazol-3-yl)-6H-benzo[c]chromen-8-yl trifluoromethanesulfonate

[0186] ##STR00432##

[0187] In an analogous manner, it is possible to obtain the following compounds by method (h). The residue is recrystallized from toluene. The yield is 81% of theory,

[0188] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00013 Reactant 1 Product Yield k1 [00433] [00434] 80% k2 [00435] [00436] 78% k3 [00437] [00438] 84% k4 [00439] [00440] 73% k5 [00441] [00442] 72% k6 [00443] [00444] 71% k7 [00445] [00446] 79% k8 [00447] [00448] 72% k9 [00449] [00450] 75% k10 [00451] [00452] 74%

I) Dibenzofuran-1-yl-3-(9-phenyl-9H-carbazol-3-yl)benzo[c]chromen-6-one

[0189] ##STR00453##

[0190] In an analogous manner, it is possible to obtain the following compounds by method (j). The residue is recrystallized from toluene/heptane and finally sublimed under high vacuum (p=5×10.sup.−5 mbar, T=377° C.). The yield is 75% of theory.

[0191] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00014 Reactant 1 Product Yield l1 [00454] [00455] [00456] 80% l2 [00457] [00458] [00459] 75% l3 [00460] [00461] [00462] 78% l4 [00463] [00464] [00465] 84% l5 [00466] [00467] [00468] 73% l6 [00469] [00470] [00471] 72% l7 [00472] [00473] [00474] 71% l8 [00475] [00476] [00477] 79% l9 [00478] [00479] [00480] 72% l10 [00481] [00482] [00483] 75% l11 [00484] [00485] [00486] 74% l12 [00487] [00488] [00489] 73% l13 [00490] [00491] [00492] 74%

m) 8-(12,12-Dimethyl-12H-10-azaindeno[2,1-b]fluoren-10-yl)benzo[c]chromen-6-one

[0192] ##STR00493##

[0193] 31 g (115 mmol) of 8-bromo-6H-dibenzo[b,d]pyran-6-one, 27.7 g (98 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene 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 subjected to hot extraction with toluene, recrystallized from toluene and finally sublimed under high vacuum. The purity is 99.9% by HPLC. The yield is 33 g (69 mmol), corresponding to 71% of theory.

[0194] The following compounds can be prepared in an analogous manner:

TABLE-US-00015 Reactant 1 Reactant 2 Product Yield m1 [00494] [00495] [00496] 70% m2 [00497] [00498] [00499] 74% m3 [00500] [00501] [00502] 81% m4 [00503] [00504] [00505] 80% m5 [00506] [00507] [00508] 79% m6 [00509] [00510] [00511] 62% m7 [00512] [00513] [00514] 75% m8 [00515] [00516] [00517] 79% m9 [00518] [00519] [00520] 81% m10 [00521] [00522] [00523] 78%

[0195] Production of the OLEDs

[0196] In use examples R1 to R16 which follow (see tables 1 and 2), the data of various OLEDs are presented.

[0197] Pretreatment for Examples R1-R16:

[0198] Glass plaques 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 Al 4083 from Heraeus Precious Metals GmbH, Germany, spun on from aqueous solution). These coated glass plaques form the substrates to which the OLEDs are applied.

[0199] The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/optional 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 1. The materials required for production of the OLEDs are shown in Table 3.

[0200] 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:IC3:TEG1 (55%:35%:10%) mean here that the material IC1 is present in the layer in a proportion by volume of 55%, IC3 in a proportion of 35% and TEG1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0201] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. The parameter U1000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/mm.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

[0202] The data for the various OLEDs are collated in Table 2. Examples R1-R16 show data for OLEDs of the invention. The structures of the invention are used here as matrix material in the emission layer (EML) and for conduction of electrons in the electron transport layer (ETL). In addition, the structures of the invention can be used as hole blocker layer (HBL).

TABLE-US-00016 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness R1 SpA1 HATCN SpMA1 EG1:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R2 SpA1 HATCN SpMA1 EG2:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R3 SpA1 HATCN SpMA1 EG3:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R4 SpA1 HATCN SpMA1 EG4:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R5 SpA1 HATCN SpMA1 IC1:TEG1 IC1 EG5:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R6 SpA1 HATCN SpMA1 IC1:TEG1 IC1 EG6:ST2 LiF 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (60%:40%) 1 nm 30 nm R7 SpA1 HATCN SpMA1 EG7:IC3:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (65%:30%:5%) 30 nm 10 nm (50%:50%) 30 nm R8 SpA1 HATCN SpMA1 EG8:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R9 SpA1 HATCN SpMA1 IC1:TEG1 EG9 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R10 SpA1 HATCN SpMA1 IC1:TEG1 IC1 EG10:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R11 HATCN SpMA1 SpMA2 IC1:EG11:TEY1 — ST2 LiQ 5 nm 70 nm 15 nm (45%:45%:10%) 25 nm 45 nm 3 nm R12 HATCN SpMA1 SpMA2 L1:EG12:TEY1 — ST2 LiQ 5 nm 70 nm 15 nm (45%:45%:10%) 25 nm 45 nm 3 nm R13 SpA1 HATCN SpMA1 EG13:TER3 — ST2:LiQ — 90 nm 5 nm 130 nm (92%:8%) 40 nm (50%:50%) 40 nm R14 SpA1 HATCN SpMA1 IC1:TEG1 IC1 EG14:LiQ — 70nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R15 SpA1 HATCN SpMA1 EG15:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm R16 SpA1 HATCN SpMA1 EG16:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm

TABLE-US-00017 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 R1 3.6 57 50 15.7% 0.31/0.64 R2 3.3 58 55 15.5% 0.33/0.64 R3 3.6 56 49 15.4% 0.34/0.62 R4 3.4 60 55 16.1% 0.33/0.63 R5 3.4 64 59 17.2% 0.33/0.63 R6 3.6 64 56 17.4% 0.32/0.64 R7 3.4 57 53 15.5% 0.30/0.65 R8 3.3 60 57 16.5% 0.32/0.64 R9 3.5 61 55 17.2% 0.32/0.63 R10 3.3 64 61 17.0% 0.34/0.63 R11 2.9 84 91 25.1% 0.45/0.54 R12 3.1 82 83 24.0% 0.43/0.56 R13 4.7 11 7 12.2% 0.67/0.33 R14 3.5 60 54 17.0% 0.33/0.62 R15 3.3 58 55 15.6% 0.33/0.63 R16 3.2 57 56 15.3% 0.32/0.64

TABLE-US-00018 TABLE 3 Structural formulae of the materials for the OLEDs [00524] HATCN [00525] SpA1 [00526] SpMA1 [00527] LiQ [00528] TEG1 [00529] TEY1 [00530] L1 [00531] ST2 [00532] TER3 [00533] SpMA2 [00534] IC1 [00535] IC3 [00536] EG1 [00537] EG2 [00538] EG3 [00539] EG4 [00540] EG5 [00541] EG6 [00542] EG7 [00543] EG8 [00544] EG9 [00545] EG10 [00546] EG11 [00547] EG12 [00548] EG13 [00549] EG14 [00550] EG15 [00551] EG16