COMPOUNDS FOR ELECTRONIC DEVICES

Abstract

The present application relates to compounds of the formula (1), to processes for preparing these compounds, to the use of these compounds in electronic devices and to electronic devices containing at least one of these compounds.

Claims

1.-19. (canceled)

20. A compound of a formula (I) ##STR00709## wherein the amino group shown with a variable bond position at the spirobifluorene in formula (I) is bonded either to Z.sup.1 or to Z.sup.2; and wherein the following applies for the groups and indices that occur: A is C or Si; 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 each substituted by R.sup.2 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are each substituted by R.sup.2 radicals; Ar.sup.1 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 24 aromatic ring atoms and are substituted by R.sup.3 radicals, and heteroaromatic ring systems which have 5 to 24 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 phenyl substituted by R.sup.5 radicals, naphthyl substituted by R.sup.5 radicals and heteroaromatic ring systems which have 6 to 10 aromatic ring atoms and are each substituted by R.sup.5 radicals; Ar.sup.3 is selected from groups of the formulae (Ar.sup.3-1) to (Ar.sup.3-7) which are bonded to the formula (I) via the bond marked with * ##STR00710## wherein Z.sup.4 is the same or different at each instance and is selected from CR.sup.6 and N, and wherein in formulae (Ar.sup.3-2) to (Ar.sup.3-7) the group Z.sup.4 which bonds to a freely drawn bond is C; wherein in formula (Ar.sup.3-3) X representing C(R.sup.6).sub.2 may also be bonded to the rest of formula (I), wherein a group R.sup.6 in this group X is then replaced by the bond to the rest of formula (I); and wherein X is selected from O, S, NR.sup.6 and C(R.sup.6).sub.2; and wherein in formula (Ar.sup.3-3) one or more units Z.sup.4═Z.sup.4 may be replaced by a unit selected from the units ##STR00711## wherein the atoms marked with # in each case replace the atoms Z.sup.4; and wherein in formula (Ar.sup.3-3) one or more units Z.sup.4—Z.sup.4 may be replaced by a unit selected from the units ##STR00712## wherein the atoms marked with # in each case replace the atoms Z.sup.4; Z is the same or different at each instance and is selected from CR.sup.1 and N; Z.sup.1 and Z.sup.2 are each C when the amino group shown with a variable bond position is bonded thereto and selected from CR.sup.1 and N; Z.sup.3 is the same or different at each instance and is selected from CR.sup.4 and N; 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.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, —(Ar.sup.L).sub.k—N(Ar.sup.4).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 radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 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.7 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.7C═CR.sup.7—, —C≡C—, Si(R.sup.7).sub.2, C═O, C═NR.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, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are each the same or different at each instance and are 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 radicals R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 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.7 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.7C═CR.sup.7—, —C≡C—, Si(R.sup.7).sub.2, C═O, C═NR.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; Ar.sup.4 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 one or more R.sup.7 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by one or more R.sup.7 radicals; 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.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 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.8 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.8C═CR.sup.8—, —C≡C—, Si(R.sup.8).sub.2, C═O, C═NR.sup.8, —C(═O)O—, —C(═O)NR.sup.8—, NR.sup.8, P(═O)(R.sup.8), —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, 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 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; k is 0, 1, 2, 3 or 4; m is 0, 1, 2, 3 or 4; and n is 1, 2, 3 or 4.

21. The compound according to claim 20, wherein Z.sup.1 and Z.sup.2 are each C when the amino group shown with a variable bond position is bonded thereto and otherwise are CR.sup.1, Z is CR.sup.1, Z.sup.3 is CR.sup.4 and Z.sup.4 is CR.sup.6.

22. The compound according to claim 20, wherein R.sup.1 is the same or different at each instance and is selected from H, —[Ar.sup.L].sub.k—N(Ar.sup.4).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 the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.7 radicals.

23. The compound according to claim 20, wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 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 or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy 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 and alkoxy groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.7 radicals; and where one or more CH.sub.2 groups in the alkyl or alkoxy groups mentioned may be replaced by —C≡C—, —R.sup.7C═CR.sup.7—, Si(R.sup.7).sub.2, C═O, C═NR.sup.7, —NR.sup.7—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.7—.

24. The compound according to claim 20, wherein the compound contains at least one group R.sup.4 which is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, each of which are substituted by R.sup.7 radicals.

25. The compound according to claim 20, wherein index k is 0.

26. The compound according to claim 20, wherein Ar.sup.1 is the same or different at each instance and is selected from phenyl, naphthyl, fluorenyl and biphenyl, each substituted by R.sup.3 radicals.

27. The compound according to claim 20, wherein the compound conforms to a formula selected from the following formulae: ##STR00713## wherein the groups and indices that occur are as defined in claim 20.

28. The compound according to claim 20, wherein the compound conforms to one of the following formulae: ##STR00714## ##STR00715## wherein the indices that occur are as defined in claim 20.

29. The compound according to claim 20, wherein Ar.sup.2 is the same or different at each instance and is selected from phenyl and naphthyl, each substituted by R.sup.5 radicals.

30. The compound according to claim 20, wherein index n is 1 or 2.

31. The compound according to claim 20, wherein Ar.sup.3 is selected from groups of the formulae (Ar.sup.3-2) and (Ar.sup.3-3): ##STR00716##

32. The compound according to claim 20, wherein A is C.

33. A process for preparing the compound according to claim 20, wherein an amino group is introduced using an organometallic coupling reaction.

34. An oligomer, polymer or dendrimer containing one or more compounds according to claim 20, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 or R.sup.6 in formula (I).

35. A formulation comprising at least one compound according to claim 20 and at least one solvent.

36. An electronic device comprising at least one compound according to claim 20.

37. The electronic device according to claim 36, wherein the device 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.

38. A method comprising utilizing the compound as claimed in claim 20 in an electronic device.

Description

EXAMPLES

A) Synthesis Examples

1) Synthesis of N-[4-(naphthalene-1-yl)phenyl]-N-(4-{8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)-9,9′-spirobi[fluoren]-1-amine 1a

[0171] ##STR00486##

[0172] 16.8 g of 4-(naphthalen-1-yl)-N-(4-{8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(13),2,4,6,9,11-hexaen-6yl}phenyl)aniline (36.4 mmol), and 1-bromo-9,9′-spirobi[fluorene] (13.8 g, 34.7 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) 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% determined by HPLC. The yield is 7.1 g (26% of theory).

[0173] The following compounds are prepared in an analogous manner:

TABLE-US-00004 Ex. Br-spiro Amine Product 1b [00487] [00488] [00489] 1c [00490] [00491] [00492] 1d [00493] [00494] [00495] 1e [00496] [00497] [00498] 1f [00499] [00500] [00501] 1g [00502] [00503] [00504] 1h [00505] [00506] [00507] 1i [00508] [00509] [00510] 1j [00511] [00512] [00513] 1k [00514] [00515] [00516] 1l [00517] [00518] [00519] 1m [00520] [00521] [00522] 1n [00523] [00524] [00525] 1o [00526] [00527] [00528] 1p [00529] [00530] [00531] 1p [00532] [00533] [00534]

2) Synthesis of 1-{[4-(naphthalen-1-yl)phenyl](4-{8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)amino}-9H-fluoren-9-one 2a

[0174] ##STR00535##

[0175] N-[4-(naphthalen-1-yl)phenyl]-4-{8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(9),2(7),3,5,10,12-hexaen-6-yl}aniline (40.3 g; 87.4 mmol), 1-bromofluoren-9-one (22.6 g, 87.4 mmol) and sodium tert-pentoxide (20.2 g, 174.7 mmol) are dissolved in 700 ml of toluene. The solution is degassed and saturated with N.sub.2. It is subsequently admixed with tri-tert-butylphosphine (3.5 ml; 3.5 mmol, 1M in toluene) and 1.6 g (1.7 mmol) of Pd.sub.2(dba).sub.3. The reaction mixture is heated to boiling under a protective atmosphere overnight. The mixture is cooled and 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 yield is 49.2 g (80% of theory).

[0176] The following compounds are prepared in an analogous manner:

TABLE-US-00005 Product: Ex. Bromofluorenone Amine 1-Aminofluorenone 2b [00536] [00537] [00538] 2c [00539] [00540] [00541] 2d [00542] [00543] [00544] 2e [00545] [00546] [00547] 2f [00548] [00549] [00550] 2g [00551] [00552] [00553] 2h [00554] [00555] [00556] 2i [00557] [00558] [00559] 2j [00560] [00561] [00562]

3) Synthesis of N-[4-(naphthalen-1-yl)phenyl]-N-(4-f8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaen-6-yl)phenyl)-9,9′-spirobi[fluoren]-1-amine 1a 3a

[0177] ##STR00563##

[0178] 25 g (105.2 mmol) of 2-bromo-1,1′-biphenyl are dissolved in a baked-out flask in 300 ml of dried THF. 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) are slowly added dropwise. The mixture is stirred at −70° C. for a further 1 hour. Subsequently 49.2 g of 1-{[4-(naphthalen-1-yl)phenyl](4-{8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1 (13),2,4,6,9,11-hexaen-6-yl}phenyl)amino}-9H-fluoren-9-one (70.1 mmol) is dissolved in 300 mL of THF 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 material is dissolved in 500 ml of toluene, and then 720 mg (3.8 mmol) of p-toluenesulfonic acid are added. The mixture is heated under reflux for 6 hours, then allowed to cool down to room temperature and admixed with water. The precipitated solid is filtered off with suction and washed with heptane (40.10 g, 68% yield). The remaining residue is recrystallized from heptane/toluene. The substance is finally sublimed under high vacuum, purity is 99.9% determined by HPLC. The yield is 19.2 g (48% of theory).

[0179] The following compounds are prepared in an analogous manner:

TABLE-US-00006 Reactant: Ex. 1-Aminofluorenone Br-Biphenyl Product 3b [00564] [00565] [00566] 3c [00567] [00568] [00569] 3d [00570] [00571] [00572] 3e [00573] [00574] [00575] 3f [00576] [00577] [00578] 3g [00579] [00580] [00581]

4) Synthesis of N-[4-(naphthalen-1-yl)phenyl]-N-(4-{8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)-4-{9,9′-spirobi[fluoren]-8-yl}aniline 4a

[0180] ##STR00582##

[0181] 25.9 g (39 mmol) of 4-(naphthalen-1-yl)-N-(4-{8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]aniline and 16.6 g (42 mmol) of 8-bromo-9,9′-spirobi[fluorene] 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 are 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% determined by HPLC. The yield is 11 g (33% of theory).

[0182] The following compounds are prepared in an analogous manner:

TABLE-US-00007 Ex. Spiro Amine Product 4b [00583] [00584] [00585] 4c [00586] [00587] [00588] 4d [00589] [00590] [00591] 4e [00592] [00593] [00594] 4f [00595] [00596] [00597]

5) Synthesis of 1-(4-chloro-phenyl)-fluoren-9-one 5a

[0183] ##STR00598##

[0184] 76 g (486 mmol) of 4-chlorophenylboronic acid, 120 g (463 mmol) of 1-bromofluorene and 16 g (14 mmol) of Pd(Ph.sub.3P).sub.4 are dissolved in 1.9 L of THF. The solution is degassed and saturated with N.sub.2 and 463 ml of 2 M potassium carbonate solution are slowly added to this suspension. 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. The residue is purified by crystallization with MeOH. Yield: 125 g (93% of theory), purity by HPLC >98%.

[0185] The following compounds are prepared in an analogous manner:

TABLE-US-00008 Ex. 1-Br-Fluorenone Boronic acid Product 5b [00599] [00600] [00601] 5c [00602] [00603] [00604] 5d [00605] [00606] [00607] 5e [00608] [00609] [00610]

6) Synthesis of 1-(4-{[4-(naphthalen-1-yl)phenyl](4-{8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)amino}phenyl)-9H-fluoren-9-one 6a

[0186] ##STR00611##

[0187] N-[4-(naphthalen-1-yl)phenyl]-4-{8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(9),2(7),3,5,10,12-hexaen-6-yl}aniline (32 g, 69 mmol),1-1-(4-chlorophenyl)-fluoren-9-one, (20 g, 69 mmol) and sodium tert-butoxide (9.5 g, 138 mmol) are dissolved in 300 mL of toluene. The solution is degassed and saturated with N.sub.2. It is subsequently admixed with tri-tert-butylphosphine (2 ml, 2 mmol, 1 M in toluene) and 0.98 g (1 mmol) of Pd.sub.2(dba).sub.3. The reaction mixture is heated to boiling under a protective atmosphere overnight. The mixture is cooled and 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 yield is 43 g (87% of theory).

[0188] The following compounds are prepared in an analogous manner:

TABLE-US-00009 Ex. Fluorenone Amine Product 6b [00612] [00613] [00614] 6c [00615] [00616] [00617] 6d [00618] [00619] [00620] 6f [00621] [00622] [00623] 6g [00624] [00625] [00626]

7) Synthesis of N-[4-(naphthalen-1-yl)phenyl]-N-(4-{8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)-4-{9,9′-spirobi[fluoren]-8-yl}aniline 7a

[0189] ##STR00627##

[0190] 17 g (73 mmol) of 2-bromo-1,1′-biphenyl are dissolved in a baked-out flask in 90 ml of dried THF. The reaction mixture is cooled to −78° C. At this temperature, 165 ml of a 2.5 M solution of n-BuLi in hexane (66 mmol) are slowly added dropwise. The mixture is stirred at −70° C. for a further 1 hour. Subsequently 50 g of 1-(4-{[4-(naphthalen-1-yl)phenyl](4-{8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)amino}phenyl)-9H-fluoren-9-one (70.1 mmol) are dissolved in 300 ml of THF 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 material is dissolved in 500 ml of toluene, and then 720 mg (3.8 mmol) of p-toluenesulfonic acid are added. The mixture is heated under reflux for 6 hours, then allowed to cool down to room temperature and admixed with water. The precipitated solid is filtered off with suction and washed with heptane (40.10 g, 66% yield).

[0191] The remaining residue is recrystallized from heptane/toluene. The substance is finally sublimed under high vacuum, purity is 99.9% determined by HPLC. The yield is 28 g (48% of theory).

[0192] The following compounds are prepared in an analogous manner:

TABLE-US-00010 Ex. 1-Aminefluorenone Br-Biphenyl Product 7b [00628] [00629] [00630] 7c [00631] [00632] [00633] 7d [00634] [00635] [00636] 7e [00637] [00638] [00639]

8) Synthesis of 8′-(4-chlorophenyl)-9,9′-spirobifluorene 8a

[0193] ##STR00640##

[0194] 10.7 g (69 mmol) of 4-chlorophenylboronic acid, 27.2 g (69 mmol) of 1-bromospiro and 5.4 g (5 mmol) of Pd(Ph.sub.3P).sub.4 are dissolved in 600 ml of THF. The solution is degassed and saturated with N.sub.2 and 155 ml of 2 M potassium carbonate solution are slowly added to this suspension. 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. The residue is purified by crystallization with MeOH. Yield: 25 g (85% of theory). Purity by HPLC >98%.

[0195] The following compounds are prepared in an analogous manner:

TABLE-US-00011 Ex. Reactant 1 Reactant 2 Product 8b [00641] [00642] [00643] 8c [00644] [00645] [00646] 8d [00647] [00648] [00649] 8e [00650] [00651] [00652]

9) Synthesis of N-((1,1′-biphenyl)-4-yl)N-(4-(2′,7′-di-tert-butyl-9,9′-spirobi(fluorene)-1-yl)phenyl)-9,9-dimethylfluoren-2-amine 9a

[0196] ##STR00653##

[0197] 10.1 g (28 mmol) of N-[4-(naphthalen-1-yl)phenyl]-4-8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1 (9),2(7),3,5,10,12-hexaen-6-yl-aniline and 14.5 g (27 mol) of the 8′-(4-chlorophenyl)-9,9′-spirobifluorene are dissolved in 225 ml of toluene. The solution is degassed and saturated with N.sub.2. It is subsequently admixed with 2.1 ml (2.1 mmol) of tri-tert-butylphosphine solution (1 M in toluene) and 0.98 g (1 mmol) of Pd.sub.2(dba).sub.3 and then 5.1 g of sodium tert-butoxide (53 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% determined by HPLC. The yield is 6 g (26% of theory).

[0198] The following compounds are prepared in an analogous manner:

TABLE-US-00012 Ex. Spirofluorene Amine Product 9b [00654] [00655] [00656] 9c [00657] [00658] [00659] 9d [00660] [00661] [00662] 9e [00663] [00664] [00665] 9f [00666] [00667] [00668] 9g [00669] [00670] [00671]

10) Synthesis of N-[4-(naphthalen-1-yl)phenyl]-N-(4-{8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)-4′-{9,9′-spirobi[fluoren]-8-yl}-[1,1′-biphenyl]-4-amine 10a

[0199] ##STR00672##

[0200] 1510.1 g (28 mmol) of N-[4-(naphthalen-1-yl)phenyl]-4-8-oxatricyclo[7.4.0.0.sup.27]trideca-1(9),2(7)3,5,10,12-hexaen-6-yl-aniline and 14.5 g (29 mmol) of the 1-{4′-chloro-[1,1′-biphenyl]-4-yl}-9,9′-spirobi[fluorene] are dissolved in 225 ml of toluene. The solution is degassed and saturated with N.sub.2. It is subsequently admixed with 2.1 ml (2.1 mmol) of tri-tert-butylphosphine solution (1 M in toluene) and 0.98 g (1 mmol) of Pd.sub.2(dba).sub.3 and then 5.1 g of sodium tert-butoxide (53 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 8 g (30% of theory).

[0201] The following compounds are prepared in an analogous manner:

TABLE-US-00013 Ex. Spirofluorene Amine Product 10b [00673] [00674] [00675] 10c [00676] [00677] [00678] 10d [00679] [00680] [00681] 10e [00682] [00683] [00684] 10f [00685] [00686] [00687] 10g [00688] [00689] [00690]

B) Device Examples

[0202] 1) General Production Process for the OLEDs and Characterization of the OLEDs

[0203] Glass plaques 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.

[0204] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport 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. The material H used here is an anthracene derivative, and the material SEB used is a spirobifluorenediamine. The p-dopant used is NDP-9 from Novaled-AG, Dresden.

[0205] 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%. Analogously, 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.

[0206] 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 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.

[0207] 2) Inventive OLEDs Containing a Compound of the Formula (I) in the EBL of Blue-Fluorescing OLEDs: Comparison of the Inventive Substitution Positions 1 and 2 with the Substitution Positions 3 and 4

[0208] Devices as shown in the following table are produced:

TABLE-US-00014 HIL HTL EBL EML HBL ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm nm E1 HTM: p-dopant HTM HTM-1 H: SEB(3%) HBM 10 nm ETM: LIQ(50%) LIQ (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 10 nm E2 HTM: p-dopant HTM HTM-2 H: SEB(3%) HBM 10 nm ETM: LIQ(50%) LiQ (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 10 nm E-C1 HTM: p-dopant HTM HTM-C1 H: SEB(3%) HBM 10 nm ETM: LIQ(50%) LiQ (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 10 nm E-C2 HTM: p-dopant HTM HTM-C2 H: SEB(3%) HBM 10 nm ETM: LIQ(50%) LiQ (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 10 nm

[0209] Compounds according to the present application are employed in the OLEDs E1 and E2. OLEDs E-C1 and E-C2 serve as a reference and contain compounds substituted by the amino group at positions 3 or 4 of the spiro.

[0210] According to measurements the inventive OLEDs (substitution position 1 or 2 at the spirobifluorene) exhibit an improved lifetime compared to the OLEDs E-C1 and E-C2 with substitution positions 3 or 4 for the amino group at the spirobifluorene:

TABLE-US-00015 LT90 @ 60 mA/cm.sup.2 (h) E1 210 E2 240 E-C1 180 E-C2 180

[0211] 3) Use of the Inventive Compounds in the EBL of Green-Phosphorescing OLEDs

[0212] The following OLEDs are produced:

TABLE-US-00016 HIL HTL EBL EML HBL ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm nm E-3 HTM: p- HTM HTM-1 TMM-1(32%) TMM- HBM 10 nm ETM: LIQ(50%) LiQ dopant (5%) 90 nm 20 nm 2(60%) TEG (8%) 30 nm 1 nm 20 nm 30 nm E-4 HTM: p- HTM HTM-2 TMM-1(32%) TMM- HBM 10 nm ETM: LIQ(50%) LiQ dopant (5%) 90 nm 20 nm 2(60%) TEG (8%) 30 nm 1 nm 20 nm 30 nm E-5 HTM: p- HTM HTM-3 TMM-1(32%) TMM- HBM 10 nm ETM: LIQ(50%) LiQ dopant (5%) 90 nm 20 nm 2(60%) TEG (8%) 30 nm 1 nm 20 nm 30 nm

[0213] The inventive compounds HTM-1 to HTM-3 achieve good performance data in respect of lifetime (90-120 h LT90@80 mA), operating voltage (3.5V-3.9V U@10 mA) and efficiency (22.2-24.4% EQE@10 mA).

[0214] 4) Use of the Inventive Compounds in the HIL and HTL of Blue-Fluorescing OLEDs

[0215] The following OLEDs are produced:

TABLE-US-00017 HIL HTL EBL EML HBL ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm nm E-6 HTM-1: p-dopant HTM-1 EBM H: SEB(3%) HBM 10 nm ETM: LIQ(50%) LiQ (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 10 nm E-7 HTM-2: p-dopant HTM-2 EBM H: SEB(3%) HBM 10 nm ETM: LIQ(50%) LiQ (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 10 nm

[0216] The inventive compounds achieve good performance data in particular in respect of efficiency (8.0-9.0% EQE@10 mA) at an operating voltage of 4.0-8.0 V U@10 mA.

[0217] 5) Use of the Inventive Compounds in the EBL of Blue-Fluorescing OLEDs

[0218] The following OLED is produced:

TABLE-US-00018 Ex. HIL HTL1 HTL2 EBL EML ETL EIL E-8 HTM-A: p- HTM-A HTM-4: p- HTM-4 H-1: SEB- ETM-1: LiQ dopant (5%) 160 nm dopant (5%) 10nm 1(5%) LiQ(50%) 1 nm 20 nm 20nm 20 nm 30 nm

[0219] The inventive compound HTM-4 achieves good results. The lifetime LT90@60 mA is 210 h, the efficiency EQE@10 mA is about 8% and the voltage U@10 mA is about 4 V.

TABLE-US-00019 TABLE 3 Structures of the compounds [00691] HTM-1 [00692] HTM-2 [00693] HTM-3 [00694] HTM-4 [00695] HTM-C1 [00696] HTM-C2 [00697] HTM [00698] EBM [00699] TMM-1 [00700] TMM-2 [00701] TEG [00702] ETM [00703] LiQ [00704] HBM [00705] H-1 [00706] ETM-1 [00707] SEB-1 [00708] HTM-A