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MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

20200006657 ยท 2020-01-02

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Inventors

Cpc classification

International classification

Abstract

The present invention relates to a process to produce compounds of the formula (1) which are suitable for use in electronic devices, as well as to intermediate compounds of formula (Int-1) and compounds of formula (1-1) and (1-2) obtained via the process. These compounds are particularly suitable for use organic electroluminescent devices. The present invention also relate to electronic devices, which comprise these compounds.

Claims

1.-17. (canceled)

18. A compound of formula (Int-1), ##STR00687## where the symbols V, Ar.sup.L, X.sup.2 and the index n have the same meaning as in claim 18 where the following applies to the symbols used: V is CR or N, with the proviso that there are maximum three N per 6-membered-ring, or two adjacent groups V (V-V or VV) stand for a group of the formula (V-1) or (V-2), ##STR00688## in which the dashed bonds indicate the linking to the spirobifluorene skeleton; E is a divalent bridge selected from N(R.sup.0), B(R.sup.0), O, C(R.sup.0).sub.2, Si(R.sup.0).sub.2, CNR.sup.0, CC(R.sup.0).sub.2, S, SO, SO.sub.2, P(R.sup.0) and P(O)R.sup.0; Ar.sup.L is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1; R.sup.1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CHO, CN, C(O)Ar.sup.3, P(O)(Ar.sup.3).sub.2, S(O)Ar.sup.3, S(O).sub.2Ar.sup.3, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.3, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, CO, CS, CSe, P(O)(R.sup.3), SO, SO.sub.2, O, S or CONR.sup.3 and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3, where two adjacent substituents R.sup.1 may optionally form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R.sup.3; R.sup.3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CHO, CN, C(O)Ar.sup.3, P(O)(Ar.sup.3).sub.2, S(O)Ar.sup.3, S(O).sub.2Ar.sup.3, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.4, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, CO, CS, CSe, P(O)(R.sup.4), SO, SO.sub.2, O, S or CONR4 and where one or more H atoms may be replaced by D, F, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R4, and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R4, where two adjacent substituents R3 may optionally form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R.sup.4; R.sup.4 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by SO, SO.sub.2, O, S and where one or more H atoms may be replaced by D or F, and aromatic or heteroaromatic ring system having 5 to 24 C atoms; Ar.sup.3 is selected, identically or differently on each occurrence, from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, more preferably having 5 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.sup.4; n is 1, 2 or 3; X.sup.2 is Cl, Br, I, trifluoromethanesulfonate (CF.sub.3SO.sub.3), tosylate (CH.sub.3C.sub.6H.sub.4SO.sub.3) or mesylate (CH.sub.3SO.sub.3); X.sup.3 is Cl, Br, I or B(OR.sup.B).sub.2; with the proviso that one of the group X.sup.1 or X.sup.3 must stand for B(OR.sup.B).sub.2 but not both groups stand for B(OR.sup.B).sub.2 at the same time; and M is Lithium or Magnesium.

19. The compound according to claim 18, characterized in that X.sup.2 is Br, Cl or I.

20. The compound according to claim 18, selected from formulae (Int-2) to (Int-9), ##STR00689## ##STR00690## where the symbols have the same meaning as defined in claim 18.

21. The compound according to claim 18, selected from the compounds of formulae (Int-2-1) to (Int-2-8), ##STR00691## ##STR00692## where the symbols have the same meaning as in claim 18.

22. The compound according to claim 18, selected from the compounds of formulae (Int-2-1-1) to (Int-2-8-1), ##STR00693## ##STR00694## where X.sup.2 has the same meaning as in claim 18.

23. The compound of formula (1-1) or (1-2), ##STR00695## where the symbols V, Ar.sup.1, Ar.sup.2, R.sup.1 and the index m have the same meaning as in claim 18.

24. The compound according to claim 23, selected from the compounds of formulae (1-1-1) and (1-2-1), ##STR00696## where R, R.sup.1, Ar.sup.1, Ar.sup.2 have the same meaning as in claim 18.

25. The compound according to claim 23, selected from the compounds of formula (1-1-1a) and (1-2-1a), ##STR00697## where the symbols Ar.sup.1 and Ar.sup.2 have the same meaning as in claim 18.

26. The compound according to claim 23, wherein Ar.sup.1 and Ar.sup.2 are selected, identically or differently on each occurrence from the groups of the following formulae (A-1) to (A-48), ##STR00698## ##STR00699## ##STR00700## ##STR00701## ##STR00702## ##STR00703## ##STR00704## where the dashed bonds indicate the bonds to the nitrogen atom, where the groups of formulae (A-1) to (A-48) may further be substituted at each free position by a group R.sup.2 as defined in claim 18, where the group R.sup.0, in formulae (A-31) to (A-34), (A-41), (A-42) and (A-44), is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, Si(R.sup.3).sub.3, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which may be substituted by one or more radicals R.sup.3, an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, where two adjacent substituents R.sup.0 may optionally form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R.sup.3.

33. Electronic device comprising at least one compound according to claim 23, selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

34. Electronic device according to claim 33, which is an organic electroluminescent device, characterised in that the at least one compound is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer or as matrix material for fluorescent or phosphorescent emitters.

35. A formulation comprising at least one compound according to claim 23 and at least one solvent.

36. A mixture comprising at least one compound according to claim 23 and at least one further compound.

Description

EXAMPLES

A) Synthesis Examples

A-1) Route (a-2)

[0154] ##STR00250##

Route (a-2-1) with X.SUP.3 .is B(OR.SUP.B.).SUB.2 .and X.SUP.1 .is Br or I

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

[0155] ##STR00251##

[0156] 76 g (486 mmol) of 4-chlorophenylboronic acid, 120 g (463 mmol) of 1-Brom-fluoren-9-one and 16 g (14 mmol) of Pd(Ph.sub.3P).sub.4 are suspended in 1900 ml of THF. 463 ml of 2 M potassium carbonate solution are slowly added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 500 ml of water and subsequently evaporated to dryness. The residue is purified by crystallitation with MeOH. Yield: 125 g (420 mmol), 90% of theory, purity according to HPLC >98%.

TABLE-US-00004 Reactant 1 Reactant 2 Product Yield 1-2 [00252]embedded image [00253]embedded image [00254]embedded image 89% 1-3 [00255]embedded image [00256]embedded image [00257]embedded image 88% 1-4 [00258]embedded image [00259]embedded image [00260]embedded image 85% 1-5 [00261]embedded image [00262]embedded image [00263]embedded image 89% 1-6 [00264]embedded image [00265]embedded image [00266]embedded image 78% 1-7 [00267]embedded image [00268]embedded image [00269]embedded image 75% 1-8 [00270]embedded image [00271]embedded image [00272]embedded image 80% 1-9 [00273]embedded image [00274]embedded image [00275]embedded image 76% 1-10 [00276]embedded image [00277]embedded image [00278]embedded image 82% 1-11 [00279]embedded image [00280]embedded image [00281]embedded image 87% 1-12 [00282]embedded image [00283]embedded image [00284]embedded image 84% 1-13 [00285]embedded image [00286]embedded image [00287]embedded image 80% 1-14 [00288]embedded image [00289]embedded image [00290]embedded image 77% 1-15 [00291]embedded image [00292]embedded image [00293]embedded image 76% 1-16 [00294]embedded image [00295]embedded image [00296]embedded image 85% 1-17 [00297]embedded image [00298]embedded image [00299]embedded image 84% 1-18 [00300]embedded image [00301]embedded image [00302]embedded image 81% 1-19 [00303]embedded image [00304]embedded image [00305]embedded image 79% 1-20 [00306]embedded image [00307]embedded image [00308]embedded image 86% 1-21 [00309]embedded image [00310]embedded image [00311]embedded image 89% 1-22 [00312]embedded image [00313]embedded image [00314]embedded image 83% 1-23 [00315]embedded image [00316]embedded image [00317]embedded image 83% 1-24 [00318]embedded image [00319]embedded image [00320]embedded image 82% 1-25 [00321]embedded image [00322]embedded image [00323]embedded image 80% 1-26 [00324]embedded image [00325]embedded image [00326]embedded image 85% 1-27 [00327]embedded image [00328]embedded image [00329]embedded image 84% 1-28 [00330]embedded image [00331]embedded image [00332]embedded image 83% 1-29 [00333]embedded image [00334]embedded image [00335]embedded image 78% 1-30 [00336]embedded image [00337]embedded image [00338]embedded image 85%

Route (a-2-1) with X.SUP.1 .is B(OR.SUP.B.).SUB.2 .and X.SUP.3 .is Br, I or Cl

Synthesis of 1-(4-chloro-phenyl)-fluoren-9-one 1-1 (Compound 2-1)

[0157] ##STR00339##

Synthesis Int-A

[0158] 10 g (39 mmol) of the 1-bromofluorenone, 14.7 g (58 mmol) of bis(pinacolato)diborane and 12.5 g (127 mmol) of potassium acetate are suspended in 300 ml of dioxane. 1.6 g (1.9 mmol) of 1,1-bis(diphenyl-phosphino)ferrocenepalladium(II) dichloride complex with DCM are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 400 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene (6 g, 51% yield).

Synthesis of Compound 2-1

[0159] 20 g (69 mmol) of 1-Bromo-4-iodo-benzene, 21.1 g (69 mmol) of 1-pinacolboron ester-fluoren-9-one and 2.4 g (2.1 mmol) of Pd(Ph.sub.3P).sub.4 are suspended in 300 ml of THF. 283 ml of 2 M potassium carbonate solution are slowly added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 300 ml of water and subsequently evaporated to dryness. The residue is purified by crystallitation with MeOH. Yield: 19 g (54 mmol), 78% of theory, purity according to HPLC >98%.

[0160] The following compounds are prepared analogously:

TABLE-US-00005 Reactant 1 Reactant 2 Reactant 3 Int-B Yield 2-2 [00340]embedded image [00341]embedded image [00342]embedded image [00343]embedded image 76% 2-3 [00344]embedded image [00345]embedded image [00346]embedded image [00347]embedded image 74% 2-4 [00348]embedded image [00349]embedded image [00350]embedded image [00351]embedded image 60% 2-5 [00352]embedded image [00353]embedded image [00354]embedded image [00355]embedded image 56% 2-6 [00356]embedded image [00357]embedded image [00358]embedded image [00359]embedded image 61% 2-7 [00360]embedded image [00361]embedded image [00362]embedded image [00363]embedded image 53% 2-8 [00364]embedded image [00365]embedded image [00366]embedded image [00367]embedded image 50% 2-9 [00368]embedded image [00369]embedded image [00370]embedded image [00371]embedded image 55%

Synthesis of Intermediate Int-1

Route (a-2-2): Synthesis of 1-(4-chloro-phenyl)-spirofluorene

Compound (3-1)

[0161] ##STR00372##

[0162] 16 g (64 mmol) of 2-bromo-biphenyl are initially introduced in 400 ml of THF at 78 C. 30 ml of BuLi (2 M in hexane) are added dropwise at this temperature. After 1 hour, 16.9 g (94 mmol) of 1-(4-Chloro-phenyl)-fluoren-9-one in 200 ml of THF are added dropwise. The batch is left to stir overnight at room temperature, added to ice-water and extracted with dichloromethane. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed in vacuo, and the residue is, without further purification, heated under reflux at 100 C. overnight with 30 ml of HCl and 300 ml of AcOH. After cooling, the precipitated solid is filtered off with suction, washed once with 100 ml of water, three times with 100 ml of ethanol each time and subsequently recrystallised from heptane. Yield: 17 g (56 mmol), 60%; purity approx. 98% according to .sup.1H-NMR.

TABLE-US-00006 Reactant 1 Reactant 2 Product Yield 3-2 [00373]embedded image [00374]embedded image [00375]embedded image 80% 3-3 [00376]embedded image [00377]embedded image [00378]embedded image 78% 3-4 [00379]embedded image [00380]embedded image [00381]embedded image 60% 3-5 [00382]embedded image [00383]embedded image [00384]embedded image 65% 3-6 [00385]embedded image [00386]embedded image [00387]embedded image 72% 3-7 [00388]embedded image [00389]embedded image [00390]embedded image 70% 3-8 [00391]embedded image [00392]embedded image [00393]embedded image 78% 3-9 [00394]embedded image [00395]embedded image [00396]embedded image 73% 3-10 [00397]embedded image [00398]embedded image [00399]embedded image 79% 3-11 [00400]embedded image [00401]embedded image [00402]embedded image 72% 3-12 [00403]embedded image [00404]embedded image [00405]embedded image 75% 3-13 [00406]embedded image [00407]embedded image [00408]embedded image 80% 3-14 [00409]embedded image [00410]embedded image [00411]embedded image 75% 3-15 [00412]embedded image [00413]embedded image [00414]embedded image 73% 3-16 [00415]embedded image [00416]embedded image [00417]embedded image 70% 3-17 [00418]embedded image [00419]embedded image [00420]embedded image 75% 3-18 [00421]embedded image [00422]embedded image [00423]embedded image 65% 3-19 [00424]embedded image [00425]embedded image [00426]embedded image 58% 3-20 [00427]embedded image [00428]embedded image [00429]embedded image 80% 3-21 [00430]embedded image [00431]embedded image [00432]embedded image 72% 3-22 [00433]embedded image [00434]embedded image [00435]embedded image 75% 3-23 [00436]embedded image [00437]embedded image [00438]embedded image 67% 3-24 [00439]embedded image [00440]embedded image [00441]embedded image 75% 3-25 [00442]embedded image [00443]embedded image [00444]embedded image 70% 3-26 [00445]embedded image [00446]embedded image [00447]embedded image 65% 3-27 [00448]embedded image [00449]embedded image [00450]embedded image 75% 3-28 [00451]embedded image [00452]embedded image [00453]embedded image 80% 3-29 [00454]embedded image [00455]embedded image [00456]embedded image 70% 3-30 [00457]embedded image [00458]embedded image [00459]embedded image 65% 3-31 [00460]embedded image [00461]embedded image [00462]embedded image 70% 3-32 [00463]embedded image [00464]embedded image [00465]embedded image 81 % 3-33 [00466]embedded image [00467]embedded image [00468]embedded image 79% 3-34 [00469]embedded image [00470]embedded image [00471]embedded image 83% 2-35 [00472]embedded image [00473]embedded image [00474]embedded image 77% 3-36 [00475]embedded image [00476]embedded image [00477]embedded image 85% 3-37 [00478]embedded image [00479]embedded image [00480]embedded image 80%

Route (a-1-2): Synthesis of 1-(4-chloro-phenyl)-Spirofluorene

Compound (4-1)

[0163] ##STR00481##

[0164] 16 g (103 mmol) of 4-chlorophenylboronic acid, 37 g (94 mmol) of 1-Brom-spirofluorene and 5.4 g (5 mmol) of Pd(Ph.sub.3P).sub.4 are suspended in 600 ml of THF. 155 ml of 2 M potassium carbonate solution are slowly added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 500 ml of water and subsequently evaporated to dryness. The residue is purified by crystallitation with MeOH. Yield: 29 g (65 mmol), 72% of theory, purity according to HPLC >98%.

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield 4-2 [00482]embedded image [00483]embedded image [00484]embedded image 80% 4-3 [00485]embedded image [00486]embedded image [00487]embedded image 75% 4-4 [00488]embedded image [00489]embedded image [00490]embedded image 76% 4-5 [00491]embedded image [00492]embedded image [00493]embedded image 82% 4-6 [00494]embedded image [00495]embedded image [00496]embedded image 78% 4-7 [00497]embedded image [00498]embedded image [00499]embedded image 81% 4-8 [00500]embedded image [00501]embedded image [00502]embedded image 72% 4-9 [00503]embedded image [00504]embedded image [00505]embedded image 80% 4-10 [00506]embedded image [00507]embedded image [00508]embedded image 70%

Route (a-1-1): Synthesis of 1-(4-chloro-phenyl)-spirofluorene

[0165] ##STR00509##

Synthesis of 1-Spirofluorenepinacolboronic ester (Compound 5-1) Using a Pd Catalysator

[0166] ##STR00510##

[0167] 50 g (103 mmol) of the bromospirofluorene derivative, 32 g (123 mmol) of bis(pinacolato)diborane and 30 g (309 mmol) of potassium acetate are suspended in 800 ml of dioxane. 2.5 g (3.09 mmol) of 1,1-bis(diphenyl-phosphino)ferrocenepalladium(II) dichloride complex with DCM are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 400 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene (52 g, 95% yield).

[0168] The following compounds are prepared analogously:

TABLE-US-00008 Starting material 1 Product Yield 5-2 [00511]embedded image [00512]embedded image 90% 5-3 [00513]embedded image [00514]embedded image 88% 5-4 [00515]embedded image [00516]embedded image 91% 5-5 [00517]embedded image [00518]embedded image 87%

Synthesis of 1-Spirofluorenepinacolboronic ester (Compound 6-1) Using BuLi

[0169] ##STR00519##

[0170] 50 g (126 mmol) of 1-Bromo-spirofluorene are initially introduced in 1500 ml of THF at 20 C. 56 ml of BuLi (2 M in hexane) are added dropwise at this temperature. After 4 hours, 49 g (300 mmol) of isopropoxytetramethyl-dioxaborolane are added dropwise. The batch is left to stir overnight at room temperature. When the reaction is complete, water and ethyl acetate are added, and the organic phase is separated off, dried and evaporated. The residue is purified by chromatography on silica gel. Yield: 44 g (100 mmol), 80% of theory, purity according to HPLC >98%.

TABLE-US-00009 Borylating Starting material 1 reagent Product Yield 6-1 [00520]embedded image [00521]embedded image [00522]embedded image 85% 6-2 [00523]embedded image [00524]embedded image [00525]embedded image 80% 6-3 [00526]embedded image [00527]embedded image [00528]embedded image 75% 6-4 [00529]embedded image [00530]embedded image [00531]embedded image 78%

Route (a-1-2): Synthesis of Compounds 7-1

[0171] ##STR00532##

[0172] 20.3 g (46.3 mmol) of spirofluorene pinacoleboronic ester derivative and 8.8 g (46.3 mmol) of chlorine derivative are suspended in 300 ml of dioxane and 14.1 g of caesium fluoride (92.6 mmol). 4.1 g (5.56 mmol) of bis-(tricyclohexylphosphine)palladium dichloride are added to this suspension, and the reaction mixture is heated under reflux for 24 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 100 ml of water and subsequently evaporated to dryness. The crude product is recrystallised from heptane/toluene. The yield is 15.8 g (80% of theory).

[0173] The following compounds are prepared analogously:

TABLE-US-00010 Reagent1 Reagent 2 7-2 [00533]embedded image [00534]embedded image 7-3 [00535]embedded image [00536]embedded image 7-4 [00537]embedded image [00538]embedded image 7-5 [00539]embedded image [00540]embedded image 7-6 [00541]embedded image [00542]embedded image 7-7 [00543]embedded image [00544]embedded image 7-8 [00545]embedded image [00546]embedded image 7-9 [00547]embedded image [00548]embedded image 7-10 [00549]embedded image [00550]embedded image Product Yield 7-2 [00551]embedded image 80% 7-3 [00552]embedded image 75% 7-4 [00553]embedded image 76% 7-5 [00554]embedded image 82% 7-6 [00555]embedded image 78% 7-7 [00556]embedded image 81% 7-8 [00557]embedded image 72% 7-9 [00558]embedded image 80% 7-10 [00559]embedded image 70%

Synthesis of Compound 8-1

[0174] ##STR00560##

Synthesis of Compound 8-1

[0175] 10.1 g (28 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine and 11.7 g (27 mol) of the 1-(4-chlorophenyl)-9,9spirobifluorene are dissolved in 225 ml of toluene. The solution is degassed and saturated with N.sub.2. 2.1 ml (2.1 mmol) of a 10% tri-tert-butylphosphine solution and 0.98 g (1 mmol) of Pd.sub.2(dba).sub.3 are then added, and 5.1 g of sodium tert-butoxide (53 mmol) are subsequently added. The reaction mixture is heated at the boil under a protective atmosphere for 5 h. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9% (HPLC). The yield of compound is 11.5 g (57% of theory).

[0176] The following compounds are also prepared analogously to the synthesis of compound 1.

TABLE-US-00011 Reactant 1 Reactant 2 8- 2 [00561]embedded image [00562]embedded image 8- 3 [00563]embedded image [00564]embedded image 8- 4 [00565]embedded image [00566]embedded image 8- 5 [00567]embedded image [00568]embedded image 8- 6 [00569]embedded image [00570]embedded image 8- 7 [00571]embedded image [00572]embedded image 8- 8 [00573]embedded image [00574]embedded image 8- 9 [00575]embedded image [00576]embedded image 8- 10 [00577]embedded image [00578]embedded image 8- 11 [00579]embedded image [00580]embedded image 8- 12 [00581]embedded image [00582]embedded image 8- 13 [00583]embedded image [00584]embedded image 8- 14 [00585]embedded image [00586]embedded image 8- 15 [00587]embedded image [00588]embedded image 8- 16 [00589]embedded image [00590]embedded image 8- 17 [00591]embedded image [00592]embedded image 8- 18 [00593]embedded image [00594]embedded image 8- 18 [00595]embedded image [00596]embedded image 8- 19 [00597]embedded image [00598]embedded image 8- 20 [00599]embedded image [00600]embedded image 8- 21 [00601]embedded image [00602]embedded image 8- 22 [00603]embedded image [00604]embedded image 8- 23 [00605]embedded image [00606]embedded image 8- 24 [00607]embedded image [00608]embedded image 8- 25 [00609]embedded image [00610]embedded image 8- 26 [00611]embedded image [00612]embedded image 8- 27 [00613]embedded image [00614]embedded image 8- 28 [00615]embedded image [00616]embedded image 8- 29 [00617]embedded image [00618]embedded image 8- 30 [00619]embedded image [00620]embedded image 8- 31 [00621]embedded image [00622]embedded image 8- 32 [00623]embedded image [00624]embedded image 8- 33 [00625]embedded image [00626]embedded image 8- 34 [00627]embedded image [00628]embedded image 8- 35 [00629]embedded image [00630]embedded image 8- 36 [00631]embedded image [00632]embedded image 8- 37 [00633]embedded image [00634]embedded image 8- 38 [00635]embedded image [00636]embedded image 8- 39 [00637]embedded image [00638]embedded image Product Yield 8- 2 [00639]embedded image 78% 8- 3 [00640]embedded image 82% 8- 4 [00641]embedded image 88% 8- 5 [00642]embedded image 67% 8- 6 [00643]embedded image 76% 8- 7 [00644]embedded image 70% 8- 8 [00645]embedded image 65% 8- 9 [00646]embedded image 60% 8- 10 [00647]embedded image 70% 8- 11 [00648]embedded image 68% 8- 12 [00649]embedded image 80% 8- 13 [00650]embedded image 78% 8- 14 [00651]embedded image 72% 8- 15 [00652]embedded image 83% 8- 16 [00653]embedded image 75% 8- 17 [00654]embedded image 70% 8- 18 [00655]embedded image 65% 8- 18 [00656]embedded image 76% 8- 19 [00657]embedded image 81% 8- 20 [00658]embedded image 65% 8- 21 [00659]embedded image 55% 8- 22 [00660]embedded image 73% 8- 23 [00661]embedded image 64% 8- 24 [00662]embedded image 59% 8- 25 [00663]embedded image 72% 8- 26 [00664]embedded image 67% 8- 27 [00665]embedded image 60% 8- 28 [00666]embedded image 71% 8- 29 [00667]embedded image 67% 8- 30 [00668]embedded image 78% 8- 31 [00669]embedded image 74% 8- 32 [00670]embedded image 67% 8- 33 [00671]embedded image 72% 8- 34 [00672]embedded image 66% 8- 35 [00673]embedded image 79% 8- 36 [00674]embedded image 80% 8- 37 [00675]embedded image 56% 8- 38 [00676]embedded image 62% 8- 39 [00677]embedded image 70%

B) Device Examples

[0177] OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

[0178] The data for various OLEDs are presented in Examples below (see Tables 1 to 2). The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs basically have the following layer structure: substrate/hole-injection layer (HIL)/hole-transport layer (HTL)/electron-blocking layer (EBL)/emission layer (EML)/electron-transport layer (ETL)/electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs is shown in table 1. The materials required for the production of the OLEDs are shown in table 3.

[0179] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as H1:SEB (5%) here means that material H1 is present in the layer in a proportion by volume of 95% and SEB is present in the layer in a proportion of 5%. Analogously, other layers may also consist of a mixture of two or more materials.

[0180] The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics, and the lifetime are determined. The expression EQE @ 10 mA/cm.sup.2 denotes the external quantum efficiency at an operating current density of 10 mA/cm.sup.2. LT80 @ 6000 cd/m.sup.2 is the lifetime until the OLED has dropped from its initial luminance of 6000 cd/m.sup.2 to 80% of the initial intensity to 4800 cd/m.sup.2 calculated with an acceleration factor of 1.8.

[0181] The data for the various OLEDs containing inventive and comparative materials are summarised in table 2.

Use of Compounds According to the Invention as Hole-Transport Materials in Fluorescent OLEDs

[0182] In particular, compounds according to the invention are suitable as HIL, HTL, EBL or matrix material in the EML in OLEDs. They are suitable as a single layer, but also as mixed component as HIL, HTL, EBL or within the EML. Compared with components from prior art (V1 to V9), the samples comprising the compounds according to the invention exhibit higher efficiencies and/or improved lifetimes both in singlet blue and also in triplet green.

TABLE-US-00012 TABLE 1 Structure of the OLEDs HIL HTL IL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm V1 HIM: F4TCNQ(5%) HIM HTMV1: F4TCNQ(5%) HTMV1 H1: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 10 nm 20 nm 30 nm 1 nm E1 HIM: F4TCNQ(5%) HIM HTM1: F4TCNQ(5%) HTM1 H1: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 10 nm 20 nm 30 nm 1 nm E2 HIM: F4TCNQ(5%) HIM HTM2: F4TCNQ(5%) HTM2 H1: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 20 nm 10 nm 20 nm 30 nm 1 nm

TABLE-US-00013 TABLE 2 Data for the OLEDs U EQE LT80 @ 10 mA/cm.sup.2 @ 10 mA/cm.sup.2 @ 6000 cd/m.sup.2 Ex. [V] % [h] V1 3.4 6.8 130 E1 3.4 7.2 130 E2 3.3 7.1 140

TABLE-US-00014 TABLE 3 Structures of the materials used [00678]embedded image F4TCNQ [00679]embedded image HIM [00680]embedded image H1 [00681]embedded image SEB [00682]embedded image ETM [00683]embedded image LiQ [00684]embedded image HTMV1 [00685]embedded image HTM1 [00686]embedded image HTM2

EXAMPLES

[0183] OLED devices with the structures shown in table 1 are produced. Table 2 shows the performance data of the examples described. The device is a fluorescent blue device with comparison of HTMV1 and HTM1 as material in the electron blocking layer (EBL). It can be shown, that efficiency of device E1 is better than the comparative example V1, whereas the LT is comparable. Compared to HTMV1 (V1) as EBL HTM2 (E2) shows better efficiency and better lifetime.