COMPOUNDS FOR ELECTRONIC DEVICES

Abstract

The present application relates to a compound of a formula (I) or (II), to the use thereof in electronic devices, to processes for preparing the compound, and electronic devices comprising the compound.

Claims

1.-26. (canceled)

27. Compound of formula (I) or (II) ##STR00881## where the R units are the same or different at each instance and are selected from units of the formulae (R-1) and (R-2) ##STR00882## where the units of the formula (R-1) or (R-2) are each bonded to the rest of the formula via the positions identified by *, and where: R.sup.0 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the two R.sup.0 radicals may be joined to one another and may form an aliphatic or heteroaliphatic ring, excluding formation of a heteroaromatic or aromatic ring system by the two R.sup.0 radicals together with the carbon atom to which they bind; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; Z is the same or different at each instance and is selected from CR.sup.1 and N; X is the same or different at each instance and is selected from O, S and NAr.sup.0; Ar.sup.0 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals; Ar.sup.1 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by one or more R.sup.2 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.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; R.sup.1 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form an aliphatic or heteroaliphatic ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.2 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.5 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.6 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.6 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; and in the formulae (I) and (II), at least one A group conforming to a formula (A) is bonded to at least one substructure in the formula in question that is selected from R units and the ##STR00883##  ring in the formula (I), where an A group, when bonded to an R unit, is bonded to an Ar.sup.0 or Ar.sup.1 group that binds to the R unit, and where an A group, when bonded to the ##STR00884##  ring in the formula (I), is bonded to a Z group, which is C in this case: ##STR00885## where: Ar.sup.L is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals; Ar.sup.2 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.3 radicals; E is a single bond or a divalent group selected from C(R.sup.4).sub.2, Si(R.sup.4).sub.2, N(R.sup.4), O, and S; R.sup.3 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.4 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.4 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; k is 0 or 1, where, in the case that k=0, the Ar.sup.L group is absent and the nitrogen atom of the group of the formula (A) constitutes the attachment position; and m is 0 or 1, where, in the case that m=0, the E group is absent and the Ar.sup.2 groups are not bonded to one another; n is 0 or 1, where, in the case that n=0, the E group in question is absent and the Ar.sup.L and Ar.sup.2 groups are not bonded to one another.

28. The compound according to claim 27, wherein the R unit in formula (I) and (II) conforms to the formula (R-1) ##STR00886## where the unit of the formula (R-1) is bonded to the rest of the formula via the positions identified by *.

29. The compound according to claim 27, wherein R.sup.0 is the same or different at each instance, preferably the same, and is selected from straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the alkyl groups mentioned and the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals.

30. The compound according to claim 27, wherein X is the same or different at each instance and is selected from O and S.

31. The compound according to claim 27, wherein Z is CR.sup.1.

32. The compound according to claim 27, wherein Ar.sup.0 is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzofused dibenzofuranyl, benzofused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, where the groups mentioned are each substituted by R.sup.2 radicals.

33. The compound according to claim 27, wherein Ar.sup.1 is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzofused dibenzofuranyl, benzofused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, where the groups mentioned are each substituted by R.sup.2 radicals.

34. The compound according to claim 27, wherein R.sup.1 is the same or different at each instance and is selected from H, D, Si(R.sup.5).sub.3, straight-chain alkyl groups which have 1 to 20 carbon atoms and may be deuterated, branched or cyclic alkyl groups which have 3 to 20 carbon atoms and may be deuterated, aromatic ring systems which have 6 to 40 aromatic ring atoms and may be deuterated, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be deuterated, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals that are preferably H.

35. The compound according to claim 27, wherein R.sup.2 is the same or different at each instance and is selected from H, D, Si(R.sup.5).sub.3, straight-chain alkyl groups which have 1 to 20 carbon atoms and may be deuterated, branched or cyclic alkyl groups which have 3 to 20 carbon atoms and may be deuterated, aromatic ring systems which have 6 to 40 aromatic ring atoms and may be deuterated, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be deuterated, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals that are preferably H.

36. The compound according to claim 27, wherein only one A group is present in the compound of formula (I) or (II).

37. The compound according to claim 27, wherein Ar.sup.L is the same or different at each instance and is selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which are substituted by R.sup.3 radicals.

38. The compound according to claim 27, wherein Ar.sup.2 is the same or different at each instance and is selected from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9′-dimethylfluorene and 9,9′-diphenylfluorene, 9-silafluorene, especially 9,9′-dimethyl-9-silafluorene and 9,9′-diphenyl-9-silafluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, where the monovalent groups are each substituted by one or more R.sup.3 radicals.

39. The compound according to claim 27, wherein the sum total of the indices m and n is 0.

40. The compound according to claim 27, wherein R.sup.3 is the same or different at each instance and is selected from H, D, Si(R.sup.5).sub.3, straight-chain alkyl groups which have 1 to 20 carbon atoms and may be deuterated, branched or cyclic alkyl groups which have 3 to 20 carbon atoms and may be deuterated, aromatic ring systems which have 6 to 40 aromatic ring atoms and may be deuterated, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be deuterated, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals that are preferably H.

41. The compound according to claim 27, wherein R.sup.4 is the same or different at each instance and is selected from H, D, Si(R.sup.5).sub.3, straight-chain alkyl groups which have 1 to 20 carbon atoms and may be deuterated, branched or cyclic alkyl groups which have 3 to 20 carbon atoms and may be deuterated, aromatic ring systems which have 6 to 40 aromatic ring atoms and may be deuterated, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be deuterated, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals that are preferably H.

42. The compound according to claim 27, wherein R.sup.5 is the same or different at each instance and is selected from H, D, Si(R.sup.6).sub.3, straight-chain alkyl groups which have 1 to 20 carbon atoms and may be deuterated, branched or cyclic alkyl groups which have 3 to 20 carbon atoms and may be deuterated, aromatic ring systems which have 6 to 40 aromatic ring atoms and may be deuterated, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be deuterated, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.6 radicals that are preferably H.

43. The compound according to claim 27, wherein formula (I) or (II) conforms to one of the following formulae: ##STR00887## where the variables are as defined in claim 27, and the A group, when bonded to an R unit, is bonded either to an Ar.sup.1 group or to an Ar.sup.0 group.

44. The compound according to claim 27, wherein formula (I) or (II) conforms to one of the following formulae: ##STR00888## ##STR00889## where the variables are as defined in claim 27, and where at least one A group is present per formula, which is bonded either to a ##STR00890##  ring or to an Ar.sup.1 group or to an Ar.sup.0 group as part of an NAr.sup.0 group as X.

45. The compound according to claim 27, wherein formula (I) or (II) conforms to one of the following formulae: ##STR00891## ##STR00892## ##STR00893## ##STR00894## where the variables are as defined in claim 27.

46. A process for preparing a compound according to claim 27, wherein a) a Suzuki coupling is performed in a first step, in which a heteroaromatic five-membered ring is coupled to a benzene ring bearing a carboxylic ester group; in that the carboxylic ester group is cyclized in a second step by reaction with an organometallic reagent and subsequent ring-closure reaction under acidic conditions to form a methylene bridge between the heteroaromatic five-membered ring and the benzene ring; and in that, in a third step, a compound of the formula (I) is obtained by means of a Buchwald coupling with an amine or via a Suzuki coupling with an amino-substituted aryl or heteroaryl compound; or b) a Suzuki coupling is performed in a first step, in which a heteroaromatic five-membered ring is coupled to a further heteroaromatic five-membered ring bearing a carboxylic ester group; in that the carboxylic ester group is cyclized in a second step by reaction with an organometallic reagent and subsequent ring-closure reaction under acidic conditions to form a methylene bridge between the heteroaromatic five-membered ring and the further heteroaromatic five-membered ring; and in that, in a third step, a compound of the formula (II) is obtained by means of a Buchwald coupling with an amine or via a Suzuki coupling with an amino-substituted aryl or heteroaryl compound.

47. The compound of one of the following formulae: ##STR00895## where the variables that occur are as follows: V is the same or different at each instance and is selected from reactive groups, preferably Cl, Br or I; X is the same or different at each instance and is selected from O, S and NAr.sup.0; Ar is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals; Hal is Cl, Br or I; R is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aromatic ring system having 6 to 40 aromatic ring atoms, or a substituted or unsubstituted heteroaromatic ring system having 5 to 40 aromatic ring atoms; U is a reactive group, preferably a boronic acid group or a boronic ester group; i is 0, 1, 2 or 3; t is 0 or 1; where the compounds are each substituted at the unoccupied positions on the benzene ring by an R.sup.1 radical, as defined above for formula (I) and (II); and where the other variables are as defined in claim 27.

48. An oligomer, polymer or dendrimer containing one or more compounds according to claim 27, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.0, R.sup.1, R.sup.2, R.sup.3 or R.sup.4 in formula (I) or (II).

49. A formulation comprising at least one compound according to claim 27 and at least one solvent.

50. An electronic device comprising at least one compound according to claim 27.

51. The electronic device according to claim 50, wherein the device is an organic electroluminescent device and comprises an anode, a cathode and at least one emitting layer, and wherein the compound is present in a hole-transporting layer or in an emitting layer of the device.

52. A method comprising including the compound according to claim 27 in an electronic device.

Description

A) SYNTHESIS EXAMPLES

1) Suzuki Coupling of Five-Membered Heterocyclic Ring to Benzene Ring: Synthesis of methyl 5-chloro-2-(2,5-diphenylthiophen-3-yl)benzoate 1a

[0206] ##STR00610##

[0207] 8.10 g (37.7 mmol) of 4-chloro-2-(methoxycarbonyl)phenylboronic acid and 11.9 g (37.7 mmol) of 3-bromo-2,5-diphenylthiophene are suspended in 200 ml of THE and 38 ml of a 2M potassium carbonate solution (75.5 mmol). 0.87 g (0.76 mmol) of tetrakis(triphenylphosphine)palladium is added to this suspension, and the reaction mixture is heated under reflux for 12 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 100 ml of water and then concentrated to dryness. After the crude product has been filtered through silica gel with toluene, 14.46 g (93%) of the product is obtained.

[0208] The following compounds are prepared in an analogous manner:

TABLE-US-00005 Boronic acid Halide Product Yield 1b [00611] [00612] [00613] 76% 1c [00614] [00615] [00616] 74% 1d [00617] [00618] [00619] 80% 1f [00620] [00621] [00622] 70% 1g [00623] [00624] [00625] 86% 1h [00626] [00627] [00628] 71% 1i [00629] [00630] [00631] 77% 1j [00632] [00633] [00634] 65% 1k [00635] [00636] [00637] 81% 1l [00638] [00639] [00640] 70% 1ll [00641] [00642] [00643] 71% 1m [00644] [00645] [00646] 76% 1n [00647] [00648] [00649] 81% 1o [00650] [00651] [00652] 68% 1p [00653] [00654] [00655] 80% 1q [00656] [00657] [00658] 65% 1r [00659] [00660] [00661] 72% 1s [00662] [00663] [00664] 64% 1t [00665] [00666] [00667] 76% 1u [00668] [00669] [00670] 72% 1v [00671] [00672] [00673] 67% 1x [00674] [00675] [00676] 55%

2) Addition of Organometallic Reagent onto Carboxylic Ester Group and Ring-Closure Reaction: Synthesis of 6-chloro-8,8-dimethyl-1,3-diphenyl-8H-indeno[1,2-c]thiophene 2a

[0209] ##STR00677##

[0210] 20 g (49 mmol) of m($!ED51026E-1 D9A-41 F4-9285-4DFD2B7C1560!$)ethyl 5-chloro-2-(2,5-diphenylthiophen-3-yl)benzoate are dissolved in 160 ml of t($!67D8E4CA-C946-45FF-8106-5B2290FC926F!$)etrahydrofuran and cooled to −15° C., and 65.9 ml (198 mmol) of m($!09D5D8A2-A8CA-431 B-B104-C5BDDEA1 BC3A!$)ethylmagnesium chloride, 3.0M in THE, are slowly added dropwise. Then the mixture is left to warm up to room temperature overnight. Water is gradually added to the mixture, then it is partitioned between EtOAc and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation (19 g of pale yellow oil, 96% yield).

[0211] 2($!31 FFEF0B-5813-4E63-B21 D-149E79ADD1C9!$)-[5-Chloro-2-(2,5-diphenylthiophen-3-yl)phenyl]propan-2-ol (19 g, 46.9 mmol) is dissolved in d($!4EB44934-7C24-44C3-A9B6-BD1C06D17A8B!$)ichloromethane (200 ml), then 8.2 ml (93.85 mmol) of t($!19147724-E29D-43DC-B151-7E29F23656B2!$)rifluoromethanesulfonic acid are added and the mixture is stirred for 1 h. Water is gradually added to the mixture, then it is partitioned between EtOAc and water, and the organic phase is washed with NaHCO.sub.3 and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with heptane, 14.4 g of product are isolated (79% yield).

TABLE-US-00006 Ex. Ester Product Yield 2b [00678] [00679] 81% 2c [00680] [00681] 72% 2d [00682] [00683] 33% 2e [00684] [00685] 82% 2f [00686] [00687] 80% 2g [00688] [00689] 75% 2h [00690] [00691] 75% 2i [00692] [00693] 64% 2j [00694] [00695] 60% 2k [00696] [00697] 70% 2l [00698] [00699] 80% 2m [00700] [00701] 75% 2n [00702] [00703] 80% 2o [00704] [00705] 77% 2p [00706] [00707] 82% 2q [00708] [00709] 74% 2r [00710] [00711] 68% 2s [00712] [00713] 63% 2t [00714] [00715] 72% 2u [00716] [00717] 54% 2v [00718] [00719] 69% 2x [00720] [00721] 75% 2y [00722] [00723] 45% 2z [00724] [00725] 67% 2aa [00726] [00727] 71%

3) Buchwald Coupling with Amine: Synthesis of N-{[1,1′-biphenyl]-2-15 yl}-N-(9,9-dimethyl-9H-fluoren-2-yl)-8,8-dimethyl-1,3-diphenyl-8H-indeno[1,2-c]thiophene-6-amine 3a

[0212] ##STR00728##

[0213] 13.2 g of N-{1,1′-biphenyl]-2-yl}-9,9-dimethylfluorene-2-amine (36.4 mmol) and 14 g of 6-chloro-8,8-dimethyl-1,3-diphenyl-8H-indeno[1,2-c]thiophene (34.7 mol) are dissolved in 250 ml of toluene. The solution is degassed and saturated with N2. Thereafter, 1 g (5.1 mmol) of S-Phos and 1.6 g (1.7 mmol) of Pd.sub.2(dba).sub.3 are added thereto, and then 5 g of sodium tert-butoxide (52.05 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere overnight. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The substance is finally sublimed under high vacuum; purity is 99.9%. The yield is 7.1 g (29% of theory).

[0214] The following compounds are prepared in an analogous manner:

TABLE-US-00007 Ex. Halogenated fluorene Amine Product Yield 3b [00729] [00730] [00731] 53% 3c [00732] [00733] [00734] 65% 3d [00735] [00736] [00737] 51% 3e [00738] [00739] [00740] 62% 3f [00741] [00742] [00743] 58% 3g [00744] [00745] [00746] 63% 3h [00747] [00748] [00749] 55% 3i [00750] [00751] [00752] 77% 3j [00753] [00754] [00755] 76% 3k [00756] [00757] [00758] 65% 3l [00759] [00760] [00761] 52% 3m [00762] [00763] [00764] 73% 3n [00765] [00766] [00767] 59% 3o [00768] [00769] [00770] 55% 3p [00771] [00772] [00773] 55% 3q [00774] [00775] [00776] 75% 3r [00777] [00778] [00779] 70% 3s [00780] [00781] [00782] 72% 3t [00783] [00784] [00785] 62% 3u [00786] [00787] [00788] 45% 3v [00789] [00790] [00791] 66% 3w [00792] [00793] [00794] 66% 3x [00795] [00796] [00797] 71% 3y [00798] [00799] [00800] 49% 3z [00801] [00802] [00803] 65% 3aa [00804] [00805] [00806] 73% 3ab [00807] [00808] [00809] 70% 3ac [00810] [00811] [00812] 80% 3ad [00813] [00814] [00815] 75% 3ae [00816] [00817] [00818] 50%

4) Suzuki coupling: Synthesis of N-{[1,1′-biphenyl]-4-yl}-N-(4-{8,8-dimethyl-1,3-diphenyl-8H-indeno[1,2-c]thiophen-6-yl}phenyl)-9,9-dimethyl-9H-fluorene-2-amine 4a

[0215] ##STR00819##

[0216] 20.0 g (39 mmol) of N-{[1,1′-biphenyl]-4-yl}9,9-dimethyl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-9H-fluorene-2-amine and 16.2 g (42 mmol) of 6-chloro-8,8-dimethyl-1,3-diphenyl-8H-indeno[1,2-c]thiophene are suspended in 400 ml of dioxane and 13.7 g of caesium fluoride (90 mmol). 4.0 g (5.4 mmol) of bis(tricyclohexylphosphine)palladium dichloride is added to this suspension, and the reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 80 ml of water and then concentrated to dryness. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene and finally sublimed under high vacuum; purity is 99.9%. The yield is 11 g (33% of theory).

[0217] The following compounds are prepared in an analogous manner:

TABLE-US-00008 Halogenated Ex. fluorene Amine Product Yield 4b [00820] [00821] [00822] 53% 4c [00823] [00824] [00825] 65% 4d [00826] [00827] [00828] 50% 4e [00829] [00830] [00831] 53% 4f [00832] [00833] [00834] 60% 4g [00835] [00836] [00837] 55% 4h [00838] [00839] [00840] 65% 4i [00841] [00842] [00843] 54% 4j [00844] [00845] [00846] 65% 4k [00847] [00848] [00849] 45% 4l [00850] [00851] [00852] 80% 4m [00853] [00854] [00855] 67% 4n [00856] [00857] [00858] 60% 4o [00859] [00860] [00861] 50% 4p [00862] [00863] [00864] 62%

B) DEVICE EXAMPLES

[0218] 1) General Production Process for the OLEDs and Characterization of the OLEDs

[0219] Glass plaques which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm are the substrates to which the OLEDs are applied.

[0220] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/electron transport layer, optionally with second layer (ETL)/electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in the tables which follow. The materials used for production of the OLEDs are shown in a table below.

[0221] All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer consists of at least one matrix material (host material) and an emitting dopant which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as H:SEB (95%:5%) mean here that the material H is present in the layer in a proportion by volume of 95% and SEB in a proportion of 5%.

[0222] In an analogous manner, the electron transport layer and the hole injection layer also consist of a mixture of two materials. The structures of the materials that are used in the OLEDs are shown in Table 3.

[0223] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in %) as a function of the luminance, calculated from current-voltage-luminance characteristics assuming Lambertian radiation characteristics, and the lifetime are determined. The parameter EQE@10 mA/cm.sup.2 refers to the external quantum efficiency which is attained at 10 mA/cm.sup.2. The parameter U@10 mA/cm.sup.2 refers to the operating voltage at 10 mA/cm.sup.2. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion in the course of operation with constant current density. An LT80 FIGURE means here that the lifetime reported corresponds to the time after which the luminance has dropped to 80% of its starting value. The FIGURE @60 or 40 mA/cm.sup.2 means here that the lifetime in question is measured at 60 or 40 mA/cm.sup.2.

[0224] 2) Inventive OLEDs Containing a Compound of the Formula (I) in the EBL of Green-Phosphorescing OLEDs

[0225] Devices as shown in the following table are produced:

TABLE-US-00009 TABLE 1a Construction of the device HIL HTL EBL EML ETL ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm |1-1 HTM:p-dopant HTM HTM-1 TMM-1:TMM-2 ETM ETM:LiQ LiQ (5%) 20 nm 220 nm 10 nm (88%):TEG(12%) 10 nm (50%) 1 nm 30 nm 30 nm

[0226] In the device setup shown above, the compounds of the invention give very good efficiencies and lifetimes for the OLEDs:

TABLE-US-00010 TABLE 2a Data of the OLEDs U @ 10 mA/cm.sup.2 EQE @ 10 mA/cm.sup.2 LT80 @ 40 mA/cm.sup.2 (V) (%) (h) I1-1 3.55 14.9 374

[0227] In addition, it is possible to produce the following OLEDs containing one of compounds HTM-2 to HTM-5 in place of compound HTM-1:

TABLE-US-00011 TABLE 1a-a Construction of the device HIL HTL EBL EML ETL ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm |1-2 HTM:p-dopant (5%) HTM HTM-2 TMM-1:TMM-2 ETM ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm (88%):TEG(12%) 10 nm 30 nm 1 nm 30 nm |1-3 HTM:p-dopant (5%) HTM HTM-3 TMM-1:TMM-2 ETM ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm (88%):TEG(12%) 10 nm 30 nm 1 nm 30 nm |1-4 HTM:p-dopant (5%) HTM HTM-4 TMM-1:TMM-2 ETM ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm (88%):TEG(12%) 10 nm 30 nm 1 nm 30 nm |1-5 HTM:p-dopant (5%) HTM HTM-5 TMM-1:TMM-2 ETM ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm (88%):TEG(12%) 10 nm 30 nm 1 nm 30 nm

[0228] For these OLEDs too, very good efficiencies and lifetimes can be obtained.

[0229] 3) Inventive OLEDs Containing a Compound of the Formula (I) in the EBL of Blue-Fluorescing OLEDs

[0230] Devices as shown in the following table are produced:

TABLE-US-00012 TABLE 1b Construction of the device HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm |2-1 HTM:p-dopant (5%) HTM HTM-1 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm

[0231] In the device setup shown above, the compounds of the invention give very good efficiencies and lifetimes for the OLEDs:

TABLE-US-00013 TABLE 2b Data of the OLEDs U @ 10 mA/cm.sup.2 EQE @ 10 mA/cm.sup.2 LT80 @ 60 mA/cm.sup.2 (V) (%) (h) I2-1 3.83 7.54 207

[0232] In addition, it is possible to produce the following OLEDs containing one of compounds HTM-2 to HTM-5 in place of compound HTM-1:

TABLE-US-00014 TABLE 1b-a Construction of the device HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm |2-2 HTM:p-dopant (5%) HTM HTM-2 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm |2-3 HTM:p-dopant (5%) HTM HTM-3 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm |2-4 HTM:p-dopant (5%) HTM HTM-4 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm |2-5 HTM:p-dopant (5%) HTM HTM-5 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm

[0233] For these OLEDs too, very good efficiencies and lifetimes can be obtained.

[0234] 4) Inventive OLEDs Containing a Compound of the Formula (I) in the HIL and HTL of Blue-Fluorescing OLEDs

[0235] Devices as shown in the following table are produced:

TABLE-US-00015 TABLE 1c Structure of the OLEDs HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm |3 HTM-1:p-dopant (5%) HTM-1 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm

[0236] In the device setup shown above, the compounds of the invention give very good efficiencies and lifetimes for the OLEDs:

TABLE-US-00016 TABLE 2c Data of the OLEDs U @ 10 mA/cm.sup.2 EQE @ 10 mA/cm.sup.2 LT80 @ 60 mA/cm.sup.2 (V) (%) (h) I3-1 4.4 6.99 107

[0237] In addition, it is possible to produce the following OLEDs containing one of compounds HTM-2 to HTM-5 in place of compound HTM-1:

TABLE-US-00017 TABLE 1c-a Structure of the OLEDs HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm |3-2 HTM-2:p-dopant (5%) HTM-2 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm |3-3 HTM-3:p-dopant (5%) HTM-3 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm |3-4 HTM-4:p-dopant (5%) HTM-4 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm |3-5 HTM-5:p-dopant (5%) HTM-5 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm

[0238] For these OLEDs too, very good efficiencies and lifetimes can be obtained.

TABLE-US-00018 TABLE 3 Structures of the compounds [00865] [00866] [00867] [00868] [00869] [00870] [00871] [00872] [00873] [00874] [00875] [00876] [00877] [00878] [00879] [00880]