COMPOUNDS FOR ELECTRONIC DEVICES

Abstract

The present invention relates to a compound of formula (I), to its use in electronic devices, to methods for producing said compound, and to electronic devices containing the compound.

Claims

1.-20. (canceled)

21. A compound of a formula (I) ##STR00353## where Z.sup.1 is C when an R group or a group ##STR00354## is bonded thereto, and is otherwise the same or different at each instance and is selected from CR.sup.2 and N; Ar.sup.L 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.l is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals; Ar.sup.2 is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals; E is a single bond or a divalent group selected from C(R.sup.6).sub.2, C(R.sup.6).sub.2C(R.sup.6).sub.2, C(R.sup.6)C(R.sup.6), N(R.sup.6), O, and S; R.sup.1 is the same or different at each instance and is selected from F, CN, N(R.sup.7).sub.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 said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.7 radicals; R.sup.5 is the same or different at each instance and is selected from 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, and alkenyl or alkynyl groups having 2 to 20 carbon atoms; where said alkyl, alkoxy, alkenyl and alkynyl groups are each substituted by R.sup.7 radicals; and where one or more CH.sub.2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by R.sup.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sup.7, C(O)O, C(O)NR.sup.7, NR.sup.7, P(O)(R.sup.7), 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.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, NAr.sup.1Ar.sup.2, P(O)(R.sup.7).sub.2, OR.sup.7, S(O)R.sup.7, S(O).sub.2R.sup.7, 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 said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.7 radicals; and where one or more CH.sub.2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by R.sup.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sub.7, C(O)O, C(O)NR, NR.sup.7, P(O)(R.sup.7), O, S, SO or SO.sub.2; 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.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, NAr.sup.1Ar.sup.2, P(O)(R.sup.7).sub.2, OR.sup.7, S(O)R.sup.7, S(O).sub.2R.sup.7, 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 said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.7 radicals; and where one or more CH.sub.2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by R.sup.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sub.7, C(O)O, C(O)NR, NR.sup.7, P(O)(R.sup.7), 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.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, P(O)(R.sup.7).sub.2, OR.sup.7, S(O)R.sup.7, S(O).sub.2R.sup.7, 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 said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.7 radicals; and where one or more CH.sub.2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by R.sup.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sub.7, C(O)O, C(O)NR.sup.7, NR.sup.7, P(O)(R.sup.7), 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, C(O)R.sup.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, P(O)(R.sup.7).sub.2, OR.sup.7, S(O)R.sup.7, S(O).sub.2R.sup.7, 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.6 radicals may be joined to one another and may form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.7 radicals; and where one or more CH.sub.2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by R.sup.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sup.7, C(O)O, C(O)NR.sup.7, NR.sup.7, P(O)(R.sup.7), O, 5, SO or SO.sub.2; R.sup.7 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(O)R.sup.8, CN, Si(R.sup.8).sub.3, N(R.sup.8).sub.2, P(O)(R.sup.8).sub.2, OR.sup.8, S(O)R.sup.8, S(O).sub.2R.sup.8, 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.7 radicals may be joined to one another and may form a ring; where said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted by R.sup.8 radicals; and where one or more CH.sub.2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by R.sup.8CCR.sup.8, CC, Si(R).sub.2, CO, CNR, C(O)O, C(O)NR.sup.8, NR.sup.8, P(O)(R), O, S, SO or SO.sub.2; R.sup.8 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.8 radicals may be joined to one another and may form a ring; and where said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN; m is 0 or 1, where, when m=0, E is absent, and the Ar.sup.1 and Ar.sup.2 groups are not bonded to one another; i is 0 or 1, where, in the case that i=0, the E group in question is absent and the Ar.sup.L and Ar.sup.1 groups are not bonded to one another; k is 0 or 1, where, in the case that k=0, the E group in question is absent and the Ar.sup.L and Ar.sup.2 groups are not bonded to one another; n is 0 or 1, where, when n=0, Ar.sup.L is absent, and i and k are both 0, and the fluorene and the amino group in formula (I) are bonded directly to one another; where the group ##STR00355## is bonded in the 1, 3 or 4 position of the fluorenyl group of the formula (I), where the group ##STR00356## of the formula (I) in the compound is not identical to one or both of the Ar.sup.1 and Ar.sup.2 groups in the compound; and where at least one group selected from the Ar.sup.1 and Ar.sup.2 groups is selected from the following radicals: biphenyl; terphenyl; quaterphenyl; phenanthrenyl; dibenzofuranyl; dibenzothiophenyl; carbazolyl; and phenyl, which is substituted by at least one group selected from fluorenyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, where these radicals are each substituted by R.sup.4 radicals.

22. The compound as claimed in claim 21, wherein the group ##STR00357## is bonded in the 4 position of the fluorenyl group of the formula (I).

23. The compound as claimed in claim 21, wherein Ar.sup.L is phenyl substituted by R.sup.3 radicals.

24. The compound as claimed in claim 21, wherein it conforms to one of the following formulae: ##STR00358## where the groups that occur are as defined in claim 21.

25. The compound as claimed in claim 21, wherein Ar.sup.1 and Ar.sup.2 are the same or different at each instance and are selected from the radicals benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9-dimethylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzofused dibenzofuranyl, benzofused dibenzothiophenyl, and phenyl substituted by a group selected from naphthyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidyl and triazinyl, where said radicals are each substituted by R.sup.4 radicals.

26. The compound as claimed in claim 21, wherein at least one group selected from the Ar.sup.1 and Ar.sup.2 groups is a heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is substituted by R.sup.4 radicals.

27. The compound as claimed in claim 21, wherein Ar.sup.1 and Ar.sup.2 are selected from biphenyl, terphenyl, quaterphenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, where said groups are each substituted by R.sup.4 radicals.

28. The compound as claimed in claim 21, wherein Ar.sup.1 and Ar.sup.2 are selected differently.

29. The compound as claimed in claim 21, wherein it conforms to the following formula: ##STR00359## where the groups and indices that occur are as defined in claim 21, and where the R.sup.4 groups on the benzene rings in the fluorenyl groups are H, and where the [Ar.sup.L].sub.nN group is bonded in position 1, 3 or 4 of the fluorenyl group and where Ar.sup.2 is selected from the following radicals: biphenyl; terphenyl; quaterphenyl; phenanthrenyl; dibenzofuranyl; dibenzothiophenyl; carbazolyl; and phenyl, which is substituted by at least one group selected from fluorenyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, where these radicals are each substituted by R.sup.4 radicals.

30. The compound as claimed in claim 21, wherein R.sup.1 is the same or different at each instance 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, and aromatic ring systems having 6 to 40 aromatic ring atoms; where said alkyl groups and said aromatic ring systems are each substituted by R.sup.7 radicals.

31. The compound as claimed in claim 21, wherein it conforms to one of the following formulae: ##STR00360## where the groups and indices that occur are as defined in claim 21.

32. The compound as claimed in claim 21, wherein R.sup.2 is H.

33. The compound as claimed in claim 21, wherein R.sup.5 is the same or different at each instance and is selected from straight-chain alkyl groups having 1 to 20 carbon atoms, and branched or cyclic alkyl groups having 3 to 20 carbon atoms, where said alkyl groups are each substituted by R.sup.7 radicals.

34. The compound as claimed in claim 21, wherein it conforms to formula (I) and the variables that occur, in combination together, are as follows: Z.sup.1 is C when an R.sup.1 group or the group ##STR00361## is bonded thereto, and is otherwise CR.sup.2; the group ##STR00362## is bonded in the 4 position of the fluorenyl group of the formula (I); Ar.sup.L is phenylene substituted by R.sup.3 radicals, where R.sup.3 in this case is H; Ar.sup.1 is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals; Ar.sup.2 is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.4 radicals; where at least one group selected from the Ar.sup.1 and Ar.sup.2 groups is selected from the following radicals: biphenyl; terphenyl; quaterphenyl; phenanthrenyl; dibenzofuranyl; dibenzothiophenyl; carbazolyl; and phenyl substituted by at least one group selected from fluorenyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, where these radicals are each substituted by R.sup.4 radicals; R.sup.1 is the same or different at each instance 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, and aromatic ring systems having 6 to 40 aromatic ring atoms, where said alkyl groups and said aromatic ring systems are each substituted by R.sup.7 radicals; R.sup.2 is H; R.sup.3 is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, NAr.sup.1Ar.sup.2, 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 said alkyl groups, said aromatic ring systems and said heteroaromatic ring systems are each substituted by R.sup.7 radicals; and where one or more CH.sub.2 groups in said alkyl groups may be replaced by CC, R.sup.7CCR.sup.7, Si(R.sup.7).sub.2, CO, CNR.sup.7, NR.sup.7, O, S, C(O)O or C(O)NR.sub.7; R.sup.4 and R.sup.6 are the same or different at each instance and are selected from H, D, F, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, 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 said alkyl groups, said aromatic ring systems and said heteroaromatic ring systems are each substituted by R.sup.7 radicals; and where one or more CH.sub.2 groups in said alkyl groups may be replaced by CC, R.sup.7CCR.sup.7, Si(R.sup.7).sub.2, CO, CNR.sup.7, NR.sub.7, O, S, C(O)O or C(O)NR.sup.7; R.sup.5 is the same or different at each instance and is selected from straight-chain alkyl groups having 1 to 20 carbon atoms, and branched or cyclic alkyl groups having 3 to 20 carbon atoms, where said alkyl groups are each substituted by R.sup.7 radicals; R.sup.7 is the same or different at each instance and is selected from H, D, F, CN, 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; n is 0 or 1, where, when n=0, Ar.sup.L is absent, and the fluorene and the amino group in formula (I) are bonded directly to one another; i, k and m are 0; where the group ##STR00363## of the formula (I) in the compound is not identical to one or both of the Ar.sup.1 and Ar.sup.2 groups in the compound.

35. The compound selected from the following compounds: ##STR00364## ##STR00365## ##STR00366##

36. A process for preparing a compound of the formula (I) as claimed in claim 21, wherein a fluorenyl compound bearing at least one reactive group is either a) reacted with a secondary amine in a Buchwald reaction, or b) reacted with a boronic acid-substituted tertiary amine in a Suzuki reaction, or c) reacted in a sequence of first i) Suzuki reaction with a boronic acid-substituted and halogen-substituted aromatic or heteroaromatic compound, followed by ii) Buchwald reaction of the resultant intermediate with a secondary amine, to give a compound of the formula (I).

37. A formulation comprising at least one compound as claimed in claim 21 and at least one solvent.

38. An electronic device comprising at least one compound as claimed in claim 21.

39. The electronic device as claimed in claim 38, wherein it is an organic electroluminescent device and comprises an anode, cathode and at least one emitting layer, and in that the compound is present in a hole-transporting layer or in an emitting layer of the device.

40. A method comprising including the compound as claimed in claim 21 in an electronic device.

Description

EXAMPLES

A) Synthesis Examples

Synthesis of 2-bromo-4-tert-butyl-2-chloro-4-methyl-1,1-biphenyl 1a

##STR00160##

[0202] 8.8 g (34.2 mmol) of (2-bromo-4-tert-butylphenyl)boronic acid and 12.9 g (51.3 mmol) of methyl 2-chloro-1-iodo-4-methylbenzene 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, 10.9 g (95%) of 1a is obtained.

[0203] The following compounds are prepared in an analogous manner:

TABLE-US-00001 Halide Boronic acid Product 1b [00161] [00162] [00163] 1c [00164] [00165] [00166] 1d [00167] [00168] [00169] 1f [00170] [00171] [00172] 1g [00173] [00174] [00175] 1h [00176] [00177] [00178] 1i [00179] [00180] [00181] 1j [00182] [00183] [00184] 1k [00185] [00186] [00187] 1l [00188] [00189] [00190] 1m [00191] [00192] [00193]

Synthesis of 4-bromo-7-tert-butyl-2,9,9-trimethyl-9H-fluorene 2a

##STR00194##

[0204] 20 g (55.4 mmol) of methyl 6-bromo-4-tert-butyl-4-methyl-[1,1-biphenyl]-2-carboxylate is dissolved in 160 ml of tetrahydrofuran and cooled to 15 C., and 65.9 ml (198 mmol) of 3.0M methylmagnesium chloride in THE is slowly added dropwise. The reaction mixture is allowed to come to room temperature overnight. Water is added gradually 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 (14.6 g of pale yellow oil, 73% yleld).

[0205] 2-{6-Bromo-4-tert-butyl-4-methyl-[1,1-biphenyl]-2-yl}propan-2-ol (14.6 g, 40.4 mmol) is dissolved in toluene (150 ml), 1.9 ml (2 mmol) of sulfuric acid is added and the mixture is stirred for 1 h. Water is added gradually 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, 10.9 g of 2a is isolated (79% yleld).

[0206] The following compounds are prepared in an analogous manner:

TABLE-US-00002 Ex. Ester Product 2b [00195] [00196] 2c [00197] [00198] 2d [00199] [00200] 2e [00201] [00202] 2f [00203] [00204] 2g [00205] [00206] 2h [00207] [00208] 2i [00209] [00210] 2j [00211] [00212]

Synthesis of 7-tert-butyl-4-chloro-2,9,9-trimethyl-9H-fluorene 3a

##STR00213##

[0207] 39.9 g (118 mmol) of 2-bromo-4-tert-butyl-2-chloro-4-methyl-1,1-biphenyl is dissolved in 300 ml of dried THE in a baked-out flask. The reaction mixture is cooled to 78 C. At this temperature, 39.3 ml of a 2.5 M solution of n-BuLi in hexane (98.2 mmol) is slowly added dropwise. The mixture is stirred at 70 C. for a further 1 hour. Subsequently, 17.9 g of propan-2-one (308.6 mmol) is dissolved in 300 ml of THE and added dropwise at 70 C. After the addition has ended, the reaction mixture is left to warm up gradually to room temperature, the reaction is stopped with NH.sub.4Cl, and then the mixture is concentrated on a rotary evaporator. The solid matter is dissolved in 500 ml of toluene, and then 720 mg (3.8 mmol) of p-toluenesulfonic acid is added. The mixture is heated under reflux for 6 hours, then allowed to cool down to room temperature and admixed with water. The precipitated solids are filtered off with suction and washed with heptane (31.1 g, 88% yleld).

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

TABLE-US-00003 Ex. Biphenyl Ketone Product 3b [00214] [00215] [00216] 3c [00217] [00218] [00219] 3d [00220] [00221] [00222] 3e [00223] [00224] [00225] 3f [00226] [00227] [00228] 3g [00229] [00230] [00231] 3h [00232] [00233] [00234] 3i [00235] [00236] [00237] 3j [00238] [00239] [00240]

Synthesis of N-{[1,1-biphenyl]-4-yl}-7-tert-butyl-N-(9,9-dimethyl-9H-fluoren-2-yl)-2,9,9-trimethyl-9H-fluorene-4-amine 4a

##STR00241##

[0209] 10.9 g of N-{[1,1-biphenyl]-4-yl}-9,9-dimethyl-9H-fluorene-2-amine (30.2 mmol) and 9.4 g of 7-tert-butyl-4-chloro-2,9,9-dimethyl-9H-fluorene (31.4 mol) are dissolved in 250 ml of toluene. The solution is degassed and saturated with N.sub.2. It is subsequently admixed with 1 g (5.1 mmol) of S-Phos and 1.6 g (1.7 mmol) of Pd.sub.2(dba).sub.3 and then 5 g of sodium tert-butoxide (52.05 mmol) is 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 (38% of theory).

[0210] The following compounds are prepared in an analogous manner:

TABLE-US-00004 Ex. Halide Amine 4b [00242] [00243] 4c [00244] [00245] 4d [00246] [00247] 4e [00248] [00249] 4f [00250] [00251] 4g [00252] [00253] 4h [00254] [00255] 4i [00256] [00257] 4j [00258] [00259] 4k [00260] [00261] 4l [00262] [00263] 4m [00264] [00265] 4n [00266] [00267] 4o [00268] [00269] 4p [00270] [00271] 4q [00272] [00273] 4r [00274] [00275] 4s [00276] [00277] 4t [00278] [00279] 4u [00280] [00281] 4v [00282] [00283] 4w [00284] [00285] Ex. Product 4b [00286] 4c [00287] 4d [00288] 4e [00289] 4f [00290] 4g [00291] 4h [00292] 4i [00293] 4j [00294] 4k [00295] 4l [00296] 4m [00297] 4n [00298] 4o [00299] 4p [00300] 4q [00301] 4r [00302] 4s [00303] 4t [00304] 4u [00305] 4v [00306] 4w [00307]

Synthesis of N-{[1,1-biphenyl]-4-yl}-N-[4-(7-tert-butyl-2,9,9-trimethyl-9H-fluoren-4-yl)phenyl]-9,9-dimethyl-9H-fluorene-2-amine 5a

##STR00308##

[0211] 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 12.8 g (42.9 mmol) of 7-tert-butyl-4-chloro-2,9,9-trimethyl-9H-fluorene are suspended in 400 ml of dioxane and 13.7 g of cesium 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 (40% of theory).

[0212] The following compounds are prepared in an analogous manner:

TABLE-US-00005 Ex. Halide Amine 5b [00309] [00310] 5c [00311] [00312] 5d [00313] [00314] 5e [00315] [00316] 5f [00317] [00318] 5g [00319] [00320] 5h [00321] [00322] 5i [00323] [00324] 5j [00325] [00326] 5k [00327] [00328] 5l [00329] [00330] 5m [00331] [00332] Ex. Product 5b [00333] 5c [00334] 5d [00335] 5e [00336] 5f [00337] 5g [00338] 5h [00339] 5i [00340] 5j [00341] 5k [00342] 5l [00343] 5m [00344]

B) Device Examples

1) General Production Process for the OLEDs and Characterization of the OLEDs

[0213] Glass plates which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm form the substrates to which the OLEDs are applied.

[0214] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/hole blocker layer (HBL)/electron transport layer (ETL)/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 is shown below. The materials required for production of the OLEDs are shown in a table below. The HTM material used in the HIL and the HTL is a fluorene derivative. The p-dopant used is NDP-9 from Novaled AG, Dresden.

[0215] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer 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 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%. Analogously, the electron transport layer and the hole injection layer also consist of a mixture of two materials.

[0216] 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 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 LT90 figure means here that the lifetime reported corresponds to the time after which the luminance has dropped to 90% of its starting value. The figure @80 mA/cm.sup.2 means here that the lifetime in question is measured at 80 mA/cm.sup.2.

2) Use of the Compounds in OLEDs

[0217] In the structure shown, the compounds according to the application can be used in the EBL, as shown hereinafter for compounds 5d and 4m:

TABLE-US-00006 HIL HTL EBL EML HBL ETL EIL Thickness / Thickness / Thickness / Thickness / Thickness / Thickness / Thickness / Ex. nm nm nm nm nm nm nm 1 HTM: HTM 5 d TMM-1(32%) HBM ETM: LiQ p-dopant 50 30 nm TMM-2(60%) 5 nm LiQ(50%) 1 nm (5%) nm TEG (8%) 30 nm 10 nm 35 nm 2 HTM: HTM 4 m TMM-1(32%) HBM ETM: LiQ p-dopant 50 nm 30 nm TMM-2(60%) 5 nm LiQ(50%) 1 nm (5%) TEG (8%) 30 nm 10 nm 35 nm

[0218] Very good performance data are obtained here in all cases; see the following table:

TABLE-US-00007 TABLE OLED data Ex. V EQE LT90 1 3.8 25.0 104 2 4.0 24.4 46

TABLE-US-00008 Structures of the compounds [00345] TMM-1 [00346] TMM-2 [00347] TEG [00348] ETM [00349] LiQ [00350] HBM [00351] 5d [00352] 4m