SUBSTITUTED AROMATIC AMINES FOR USE IN ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present application relates to a specific fluorene derivative, to its use in an electronic device and to an electronic device comprising said fluorene derivatives. Further, the present application relates to a process for the preparation of such fluorene compounds and to oligomers, polymers or dendrimers as well as formulations or compositions comprising one or more of said fluorene compounds.

Claims

1.-30. (canceled)

31. A compound of formula (I) ##STR00686## in which the variables are defined as follows: Z.sup.1 is, identically or differently on each occurrence, selected from CR.sup.1, CR.sup.2 and N; Z.sup.2 is, identically or differently on each occurrence, selected from CR.sup.2 and N; Ar.sup.L is selected from aromatic ring systems having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4; Ar.sup.1, Ar.sup.2 are, identically or differently, selected from aromatic ring systems having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4; E is a single bond or is a divalent group selected from C(R.sup.4).sub.2, N(R.sup.4), O, and S; R.sup.1 is selected, identically or differently on each occurrence, from Si(R.sup.5).sub.3, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms, branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the said alkyl, alkoxy and thioalkyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5; R.sup.2 is selected, identically or differently on each occurrence, 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, SCN, SF.sub.5, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CS, CNR.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.3 is selected, identically or differently on each occurrence, from H, D, F, Cl, Br, I, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, NO.sub.2, P(O)(R.sup.4).sub.2, S(O)R.sup.4, S(O).sub.2R.sup.4, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms, or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, where the said alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups may in each case be substituted by one or more radicals R.sup.5 and where one or more CH.sub.2 groups in the said alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups may in each case be replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CS, CNR.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 and where in the said alkyl, alkoxy, thioalkyl, alkenyl and alkynyl groups one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or aromatic or heteroaromatic ring systems having 6 to 30 aromatic ring atoms, where the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5, or aryloxy groups having 5 to 60 aromatic ring atoms, or arylalkyl groups having 5 to 60 aromatic ring atoms, where the said aryloxy and arylalkyl groups may in each case be substituted by one or more radicals R.sup.5, where the two radicals R.sup.3 may be connected to each other to form a ring, so that a spiro compound is built at position 9 of the fluorene group, where spirobifluorenes are excluded; R.sup.4 is, identically or differently on each occurrence, selected from H, D, F, 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 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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.4 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CS, CNR.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, identically or differently at each occurrence, selected from H, D, F, 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 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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.5 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CS, CNR.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 selected, identically or differently at each occurrence, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.6 may be connected to each other to form a ring; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by F and CN; m is 0 or 1, where in the case of m=0, the group E is not present and the groups Ar.sup.1 and Ar.sup.2 are not connected; n is 0 or 1; where in the case of n=0, the group Ar.sup.L is not present and the nitrogen atom and the fluorene group are directly connected; characterized in that at least one of groups Z.sup.1 is CR.sup.1.

32. The compound according to claim 31, wherein group Ar.sup.L is selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthyl, fluorenyl, indenofluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, which may each be substituted by one or more radicals R.sup.4.

33. The compound according to claim 31, wherein at least one of groups Ar.sup.1 and Ar.sup.2 is selected from a radical comprising at least two rings selected from aromatic and heteroaromatic rings, which radical is optionally substituted by one or more R.sup.4.

34. The compound according to claim 33, characterized in that within said radical two aromatic or heteroaromatic rings are condensed or are connected to each other via a divalent group selected from C(R.sup.4).sub.2, N(R.sup.4), O, and S.

35. The compound according to claim 33, wherein said radical comprises at least two aromatic rings.

36. The compound according to claim 31, wherein groups Ar.sup.1 and Ar.sup.2 are, identically or differently, selected from radicals each comprising at least two rings selected from aromatic and heteroaromatic rings, which radicals are each optionally substituted by one or more R.sup.4.

37. The compound according to claim 36, wherein within at least one of said radicals two aromatic or heteroaromatic rings are condensed or are connected to each other via a divalent group selected from C(R.sup.4).sub.2, N(R.sup.4), O, and S.

38. The compound according to claim 36, wherein within both of said radicals two aromatic or heteroaromatic rings are condensed or are connected to each other via a divalent group selected from C(R.sup.4).sub.2, N(R.sup.4), O, and S.

39. The compound according to claim 36, wherein said radicals comprise at least two aromatic rings.

40. The compound according to claim 31, wherein groups Ar.sup.1 and Ar.sup.2 are, identically or differently, selected from the following groups: phenyl, naphthyl-substituted phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, fluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, pyridyl, phenyl-substituted pyridyl, pyrimidyl, pyrazinyl, pyridazinyl and triazinyl, which are each optionally substituted by one or more radicals R.sup.4.

41. The compound according to claim 31, wherein m=0.

42. The compound according to claim 31, wherein it conforms to one of Formulae (I-A) to (I-G) ##STR00687## in which the variables occurring are as defined in claim 31.

43. The compound according to claim 31, wherein it conforms to one of formulae (I-A-1) to (I-G-1) ##STR00688## in which the variables occurring are as defined in claim 31.

44. The compound according to claim 31, wherein it conforms to one of formulae (I-A-2) to (I-K-2) ##STR00689## ##STR00690## in which the variables occurring are as defined in claim 31.

45. The compound according to claim 31, wherein it conforms to one of the following formulae ##STR00691## ##STR00692## in which the variables occurring are as defined in claim 31, and wherein in Formulae (I-A-2-1) and (I-H-2-1) A.sup.L is selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, which may each be substituted by one or more radicals R.sup.4.

46. The compound according to claim 31, wherein R.sup.1 is, identically or differently on each occurrence, selected from ##STR00693## in which m is 1 and E is a single bond, aromatic ring systems having 6 to 30 aromatic ring atoms, and heteroaromatic ring systems having 5 to 30 aromatic ring atoms, where the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5.

47. The compound according to claim 31, wherein R.sup.1 is, identically or differently on each occurrence, selected from ##STR00694## in which m is 1 and E is a single bond, phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, fluorenyl, especially 9,9-dimethylfluorenyl and 9,9-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, 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, each of which may optionally be substituted by one or more radicals R.sup.5.

48. The compound according to claim 31, wherein R.sup.3 is selected, identically or differently on each occurrence, from straight-chain alkyl groups having 1 to 20 C atoms, or cyclic alkyl groups having 3 to 20 C atoms, where the said alkyl groups or cyclic alkyl groups may be substituted by one or more radicals R.sup.5, or aromatic or heteroaromatic ring systems having 6 to 30 aromatic ring atoms, where the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5, where the two radicals R.sup.3 may be connected to each other to form a ring, so that a spiro compound is built at position 9 of the fluorene group, where spirobifluorenes are excluded.

49. The compound according to claim 31, wherein R.sup.3 is identically or different on each occurrence, selected from straight-chain alkyl groups having 1 to 10 C atoms, where the said alkyl groups may be substituted by one or more radicals R.sup.5, or aromatic ring systems having 6 to 24 aromatic ring atoms, where the said aromatic ring systems may in each case be substituted by one or more radicals R.sup.5, where the two radicals R.sup.3 may be connected to each other to form a ring, so that a spiro compound is built at position 9 of the fluorene group, where spirobifluorenes are excluded.

50. A process for the preparation of a compound of formula (I) according to claim 31, comprising introducing a diarylamino group by a CN coupling reaction between a fluorene derivative, which is halogenated at 2-position, and a diarylamine derivative.

51. A process for the preparation of a compound of formula (I) according to claim 31, characterized in that the compound is prepared by reacting an alkyl 5-halo-2-iodobenzoate with an arylboronic acid.

52. Process according to claim 51, comprising the following reaction steps: a) Reacting a methyl 5-halo-2-iodobenzoate of general formula (II) ##STR00695## with an arylboronic acid derivative which conforms to one of formulae (III-1) to (III-8) ##STR00696## in which R.sup.1 is, identically or differently on each occurrence, and is selected from phenyl, biphenyl, terphenyl or quaterphenyl, each of which may optionally be substituted by one or more radicals R.sup.5 as defined above; and X is Cl or Br, to obtain a 5-halobenzoate methyl ester derivative, and subsequently b) converting the ester derivative to a tertiary alcohol by using an alkyl- or aryl-magnesium halide, or phenyl-magnesium chloride, and subsequently c) performing acid-catalyzed cyclisation to obtain a fluorene derivative, which is halogenated at 2-position, and subsequently d) reacting the fluorene derivative with a diarylamine derivative to obtain a compound of formula (I).

53. A compound of formulae (IV-A) to (IV-Is) ##STR00697## ##STR00698## in which R.sup.1 is selected, identically or differently on each occurrence, from phenyl, biphenyl, terphenyl or quarterphenyl, each of which may optionally be substituted by one or more radicals R.sup.5 as defined above; R.sup.3 is selected, identically or differently on each occurrence, from methyl and phenyl, each of which may optionally be substituted by one or more radicals R.sup.5 as defined above; and X is Cl or Br.

54. A compound of formulae (IV-A) to (IV-Is) ##STR00699## ##STR00700## in which R.sup.1 is selected, identically or differently on each occurrence, from phenyl, biphenyl, terphenyl or quarterphenyl, each of which may optionally be substituted by one or more radicals R.sup.5 as defined above; R.sup.3 is selected, identically or differently on each occurrence, from methyl and phenyl, each of which may optionally be substituted by one or more radicals R.sup.5 as defined above; and X is Cl or Br and which is obtained or obtainable in reaction step c) of claim 52.

55. An oligomer, polymer or dendrimer, comprising one or more compounds of formula (I) according to claim 31, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any desired positions in formula (I) substituted by R.sup.1 to R.sup.6.

56. A composition, comprising one or more compounds of formula (I) according to claim 31 and at least one further organic functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transporting materials, electron injecting materials, hole transporting materials, hole injecting materials, electron blocking materials, hole blocking materials, wide band gap materials, delayed fluorescent emitters and delayed fluorescent hosts.

57. A formulation comprising at least one compound of formula (I) according to claim 31, and at least one solvent.

58. An electronic device, comprising at least one compound according to claim 31.

59. An organic electroluminescent device, comprising anode, cathode and at least one emitting layer, where at least one organic layer of the device, which is an emitting layer, a hole transport layer, an electron blocking layer or a hole injection layer, comprises the at least one compound of formula (I) according to claim 31.

Description

EXAMPLES

A) Synthesis Examples

[0205] The following syntheses are carried out under a protective-gas atmosphere, unless indicated otherwise. The starting materials can be purchased from ALDRICH or ABCR. The numbers in square brackets in the case of the starting materials known from the literature are the corresponding CAS numbers.

Example 1

Synthesis of 2-{[1,1-biphenyl]-2-yl}-5-bromobenzoate methyl ester 1a

[0206] ##STR00207##

[0207] 2.9 g (14.9 mmol) of (1,1-biphenyl)-2-yl-boronic acid, 4.6 g (13.6 mmol) of methyl 5-bromo-2-iodobenzoate, 314 mg (0.3 mmol, 0.02 eq.) of Pd(P(Ph.sub.3)).sub.4, 5.6 g (40.7 mmol, 3 eq.) of Na.sub.2CO.sub.3 are dissolved in 7 mL of water and 30 mL of toluene. The reaction mixture is stirred at 85 C. and agitated under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is purified by chromatography (mixture heptane/AcOEt). The product is isolated in the form of an off-white solid (4.5 g 91% of theory).

[0208] The synthesis of further derivatives is carried out analogously:

TABLE-US-00002 Boronic acid Product Yield 1b [00208] [00209] [00210] 86% 1c [00211] [00212] [00213] 84% 1d [00214] [00215] [00216] 70% 1f [00217] [00218] [00219] 80% 1g [00220] [00221] [00222] 66% 1h [00223] [00224] [00225] 81% 1i [00226] [00227] [00228] 77% 1j [00229] [00230] [00231] 85% 1k [00232] [00233] [00234] 81% 1l [00235] [00236] [00237] 80% 1ll [00238] [00239] [00240] 81% 1m [00241] [00242] [00243] 76% 1n [00244] [00245] [00246] 81% 1o [00247] [00248] [00249] 78% 1p [00250] [00251] [00252] 70% 1q [00253] [00254] [00255] 75% 1r [00256] [00257] [00258] 65%

Synthesis of 2-(2-{[1,1-biphenyl]-2-yl}-5-bromophenyl)propan-2-ol 2a

[0209] ##STR00259##

[0210] A solution of 2-{[1,1-biphenyl]-2-yl}-5-bromobenzoate methyl ester (3 g, 8.2 mmol) in THF (30 ml) is treated with 16 mL of MeMgCl (3 M in THF, 49 mmol, 6 eq.) under argon at 10 C. The reaction proceeds at 10 C. for 30 minutes and then is stirred at room temperature overnight. The reaction is quenched with a solution of saturated NH.sub.4Cl and the mixture is extracted with EtOAc. The organic phase is dried with MgSO.sub.4 and concentrated to dryness. The residue is purified by chromatography (mixture heptane/AcOEt) to isolate pure 2a (1.8 g, 61% of theory).

[0211] The following compounds are synthesized analogously:

TABLE-US-00003 Ex. Grignard reagent Product Yield 2b [00260] PhMgCl [00261] 86% 2c [00262] MeMgCl [00263] 82% 2d [00264] PhMgCl [00265] 43% 2e [00266] MeMgCl [00267] 92% 2f [00268] MeMgCl [00269] 90% 2g [00270] PhMgCl [00271] 85% 2h [00272] MeMgCl [00273] 55% 2i [00274] PhMgCl [00275] 54% 2j [00276] MeMgCl [00277] 40% 2k [00278] MeMgCl [00279] 50% 2l [00280] PhMgCl [00281] 80% 2m [00282] MeMgCl [00283] 85% 2n [00284] PhMgCl [00285] 60% 2o [00286] PhMgCl [00287] 67% 2p [00288] PhMgCl [00289] 82% 2q [00290] MeMgCl [00291] 74% 2r [00292] PhMgCl [00293] 80% 2s [00294] MeMgCl [00295] 75% 2t [00296] [00297] [00298] 85% 2u [00299] CD.sub.3MgCl [00300] 78% 2v [00301] CH.sub.3MgCl [00302] 73% 2w [00303] [00304] [00305] 80% 2x [00306] CD.sub.3MgCl [00307] 79%

Synthesis of 2-bromo-9,9-dimethyl-5-phenyl-9H-fluorene 3a

[0212] ##STR00308##

[0213] A solution of 2-(2-{[1,1-biphenyl]-2-yl}-5-bromophenyl)propan-2-ol (1.3 g, 3.5 mmol) in CH.sub.2Cl.sub.2 (26 mL) is treated with 0.54 mL of BF.sub.3.Et.sub.2O (4.6 mmol, 1.3 eq.) under argon at 0 C. The mixture is stirred for 30 minutes. The reaction is stirred at room temperature for 2 hours. The reaction is quenched with a solution of saturated NaHCO.sub.3 and the mixture is extracted with CH.sub.2Cl.sub.2. The organic phase is dried with MgSO.sub.4 and concentrated to dryness. The residue is purified by chromatography (mixture heptane/AcOEt) to isolate pure 3a (0.9 g, 72% of theory).

[0214] The following compounds are synthesized analogously:

TABLE-US-00004 Ex. Product Yield 3b [00309] [00310] 76% 3c [00311] [00312] 62% 3d [00313] [00314] 83% 3e [00315] [00316] 72% 3f [00317] [00318] 80% 3g [00319] [00320] 75% 3h [00321] [00322] 65% 3i [00323] [00324] 74% 3j [00325] [00326] 60% 3k [00327] [00328] 70% 3l [00329] [00330] 60% 3m [00331] [00332] 75% 3n [00333] [00334] 80% 3o [00335] [00336] 82% 3p [00337] [00338] 78% 3q [00339] [00340] 68% 3r [00341] [00342] 75% 3s [00343] [00344] 65% 3t [00345] [00346] 68% 3u [00347] [00348] 78% 3v [00349] [00350] 60% 3w [00351] [00352] 73% 3x [00353] [00354] 76%

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

[0215] ##STR00355##

[0216] S-Phos (1.06 g, 2.6 mmol), Pd.sub.2(dba).sub.3 (1.18 g, 1.29 mmol) and sodium tert-butoxide (48.3 g, 85.9 mmol) are added to a solution of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine (15.5 g, 42.9 mmol) and 2-bromo-9,9-dimethyl-5-phenyl-9H-fluorene (15 g, 42.9 mmol) in degassed toluene (200 ml), and the mixture is heated under reflux for 10 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from toluene/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice. The product is isolated in the form of an off-white solid (12 g, 45% of theory).

[0217] The following compounds are obtained analogously:

TABLE-US-00005 Ex. Halogenated Fluorene Amine 4b [00356] [00357] 4c [00358] [00359] 4d [00360] [00361] 4e [00362] [00363] 4f [00364] [00365] 4g [00366] [00367] 4h [00368] [00369] 4i [00370] [00371] 4j [00372] [00373] 4k [00374] [00375] 4l [00376] [00377] 4m [00378] [00379] 4n [00380] [00381] 4o [00382] [00383] 4p [00384] [00385] 4q [00386] [00387] 4r [00388] [00389] 4s [00390] [00391] 4t [00392] [00393] 4u [00394] [00395] 4v [00396] [00397] 4w [00398] [00399] 4x [00400] [00401] 4y [00402] [00403] 4z [00404] [00405] 4aa [00406] [00407] 4ab [00408] [00409] 4ac [00410] [00411] 4ad [00412] [00413] 4ae [00414] [00415] 4af [00416] [00417] 4ag [00418] [00419] 4ah [00420] [00421] 4ai [00422] [00423] 4aj [00424] [00425] 4ak [00426] [00427] 4al [00428] [00429] 4am [00430] [00431] 4an [00432] [00433] 4ao [00434] [00435] 4ap [00436] [00437] 4ao [00438] [00439] 4ap [00440] [00441] 4aq [00442] [00443] 4ar [00444] [00445] 4as [00446] [00447] 4at [00448] [00449] 4au [00450] [00451] 4av [00452] [00453] 4aw [00454] [00455] 4ax [00456] [00457] 4ay [00458] [00459] 4az [00460] [00461] 4ba [00462] [00463] 4bb [00464] [00465] Ex. Product Yield 4b [00466] 43% 4c [00467] 85% 4d [00468] 55% 4e [00469] 64% 4f [00470] 56% 4g [00471] 73% 4h [00472] 65% 4i [00473] 67% 4j [00474] 66% 4k [00475] 50% 4l [00476] 62% 4m [00477] 73% 4n [00478] 69% 4o [00479] 57% 4p [00480] 65% 4q [00481] 71% 4r [00482] 71% 4s [00483] 72% 4t [00484] 62% 4u [00485] 45% 4v [00486] 66% 4w [00487] 66% 4x [00488] 71% 4y [00489] 49% 4z [00490] 65% 4aa [00491] 73% 4ab [00492] 70% 4ac [00493] 80% 4ad [00494] 75% 4ae [00495] 60% 4af [00496] 80% 4ag [00497] 76% 4ah [00498] 54% 4ai [00499] 47% 4aj [00500] 40% 4ak [00501] 37% 4al [00502] 35% 4am [00503] 45% 4an [00504] 47% 4ao [00505] 53% 4ap [00506] 57% 4ao [00507] 43% 4ap [00508] 56% 4aq [00509] 48% 4ar [00510] 61% 4as [00511] 49% 4at [00512] 50% 4au [00513] 55% 4av [00514] 60% 4aw [00515] 64% 4ax [00516] 52% 4ay [00517] 68% 4az [00518] 70% 4ba [00519] 61% 4bb [00520] 54%

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

[0218] ##STR00521##

[0219] 59.1 g (101.8 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine, 35.5 g (101.8 mmol) of 2-bromo-9,9-dimethyl-5-phenyl-9H-fluorene, 3.88 g (5.14 mmol) of PdCl.sub.2(Cy).sub.3, 31.2 g (205.6 mmol) of cesium fluoride are dissolved in 800 mL of toluene. The reaction mixture is refluxed and agitated under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice. The product is isolated in the form of a white solid (42 g, 59% of theory).

[0220] The following compounds are synthesized analogously:

TABLE-US-00006 Ex. Halogenated Fluorene Amine 5b [00522] [00523] 5c [00524] [00525] 5d [00526] [00527] 5e [00528] [00529] 5f [00530] [00531] 5g [00532] [00533] 5h [00534] [00535] 5i [00536] [00537] 5j [00538] [00539] 5k [00540] [00541] 5l [00542] [00543] 5m [00544] [00545] 5n [00546] [00547] 5o [00548] [00549] 5p [00550] [00551] 5q [00552] [00553] 5r [00554] [00555] 5s [00556] [00557] 5t [00558] [00559] 5u [00560] [00561] Ex. Halogenated Fluorene Yield 5b [00562] 50% 5c [00563] 55% 5d [00564] 60% 5e [00565] 63% 5f [00566] 70% 5g [00567] 75% 5h [00568] 55% 5i [00569] 64% 5j [00570] 60% 5k [00571] 75% 5l [00572] 81% 5m [00573] 77% 5n [00574] 62% 5o [00575] 60% 5p [00576] 72% 5q [00577] 45% 5r [00578] 56% 5s [00579] 62% 5t [00580] 57% 5u [00581] 54%

Synthesis of 5-bromo-2-chloro-9,9-diphenyl-9H-fluorene 6a

[0221] ##STR00582##

[0222] A solution of 2,2-dibromo-4-chloro-biphenyl (84 g, 239 mmol) in THF (200 ml) is treated with 109 mL of n-BuLi (2.2 M in hexane, 239 mmol) under argon at 78 C. The mixture is stirred for 30 minutes. A solution of benzophenone (43.5 g, 239 mmol) in 150 mL THF is added dropwise. The reaction proceeds at 78 C. for 30 minutes and then is stirred at room temperature overnight. The reaction is quenched with water and the solid is filtered. Without further purification, a solution of the alcohol in 966 mL toluene and 2.9 g p-toluenesulfonic acid is refluxed overnight. After cooling, the organic phase is washed with water and the solvent is removed under vacuum. The product is isolated in the form of a white solid (60 g, 90% of theory).

[0223] The synthesis of further halogenated fluorene derivatives is carried out analogously:

TABLE-US-00007 Bromo-biphenyl Aryl-fluoenone Product Yield 6b [00583] [00584] [00585] 86% 6c [00586] [00587] [00588] 84% 6d [00589] [00590] [00591] 90% 6f [00592] [00593] [00594] 90% 6g [00595] [00596] [00597] 66% 6h [00598] [00599] [00600] 81% 6i [00601] [00602] [00603] 77% 6j [00604] [00605] [00606] 85% 6k [00607] [00608] [00609] 81% 6l [00610] [00611] [00612] 80% 6m [00613] [00614] [00615] 87% 6n [00616] [00617] [00618] 89% 6o [00619] [00620] [00621] 78% 6p [00622] [00623] [00624] 82%

Synthesis of 2-chloro-5,9,9-triphenyl-9H-fluorene 7a

[0224] ##STR00625##

[0225] 31.5 g (251 mmol) of phenyl-boronic acid, 108.4 g (251 mmol) of 5-bromo-2-chloro-9,9-diphenyl-9H-fluorene, 9.9 g (8.5 mmol) of Pd(P(Ph.sub.3)).sub.4, 66.8 g (627 mmol) of Na.sub.2CO.sub.3 are dissolved in 903 mL of water, 278 mL of ethanol and 1.9 L of toluene. The reaction mixture is refluxed and agitated under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from heptane. The product is isolated in the form of an off-white solid (100 g, 93% of theory).

[0226] The following compounds are synthesized analogously:

TABLE-US-00008 Ex. Product Boron acid Product Yield 7b [00626] [00627] [00628] 76% 7c [00629] [00630] [00631] 82% 7d [00632] [00633] [00634] 43% 7e [00635] [00636] [00637] 72% 7f [00638] [00639] [00640] 60% 7g [00641] [00642] [00643] 85% 7h [00644] [00645] [00646] 72% 7i [00647] [00648] [00649] 50% 7j [00650] [00651] [00652] 61% 7k [00653] [00654] [00655] 55% 7l [00656] [00657] [00658] 50% 7m [00659] [00660] [00661] 65%

B) Production of OLEDs

[0227] 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 herein (e. g. materials).

[0228] The data for various OLEDs are presented in examples below (see Tables 1 to 7). 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 materials required for the production of the OLEDs are shown in Table 7.

[0229] 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.

[0230] 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@60 mA/cm.sup.2 is the lifetime until the OLED has dropped from its initial luminance of i.e. 5000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4000 cd/m.sup.2 without using any acceleration factor. The data for the various OLEDs containing inventive material are summarised in Tables 2 to 6.

[0231] Use of Compounds According to the Invention in Fluorescent and Phosphorescent OLEDs

[0232] In particular, compounds according to the invention are suitable as HIL, HTL, EBL or matrix material in the EML in OLEDs. They are suitable for use as a single layer, but also for use as mixed component as HIL, HTL, EBL or within the EML.

[0233] OLED devices with the structures are shown in the following Tables 1, 3, 4 and 5. Tables 2 and 6 provide the device data.

[0234] OLEDs E1 to E27 are OLEDs according to the present application, which comprise the inventive compounds HTM-1 to HTM-14 as HTL and EBL, respectively. COMP-1 and COMP-2 are comparative examples. OLEDs E1 to E27 according to the present application all show high lifetimes, low voltage and good efficiency in singlet blue and also in triplet green devices. Particularly, as compared to the comparative examples the examples according to the invention clearly show statistically and physically significant improvements regarding efficiencies.

TABLE-US-00009 TABLE 1 Device Setup HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm E1 HTM-1: p- HTM-1 EBL H:SEB(5%) ETM:LiQ(50%) LiQ doped(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E2 HTM: p- HTM HTM-1 TMM-1: TMM- ETM:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm E3 HTM-2: p- HTM-2 EBL H:SEB(5%) ETM:LiQ(50%) LiQ doped (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E4 HTM: p- HTM HTM-2 TMM-1: TMM- ETM:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm E5 HTM-3: p- HTM-3 EBL H:SEB(5%) ETM:LiQ(50%) LiQ doped(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E6 HTM: p- HTM HTM-3 TMM-1: TMM- ETM:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm E7 HTM: p- HTM HTM-4 TMM-1: TMM- ETM:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm E8 HTM-5: p- HTM-5 EBL H:SEB(5%) ETM:LiQ(50%) LiQ doped(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E9 HTM: p- HTM HTM-5 TMM-1: TMM- ETM:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm C1 HTM: p- HTM COMP-1 TMM-1: TMM- ETM:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm E10 HTM: p- HTM HTM-7 TMM-1: TMM- ETM:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm C2 HTM: p- HTM COMP-2 TMM-1: TMM- EMT:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm E11 HTM: p- HTM HTM-9 TMM-1: TMM- ETM:LiQ(50%) LiQ doped(5%) 220 nm 10 nm 2(28%):TEG(12%) 30 nm 1 nm 20 nm 30 nm

TABLE-US-00010 TABLE 2 Data for the OLEDs LT80 @ 60/40* U EQE mA/cm.sup.2 [V] [%] [h] E1 4.1 9.1 220 E2 3.9 16.0 340* E3 4.0 9.4 190 E4 3.8 15.8 360* E5 3.9 9.0 300 E6 3.9 15.4 340* E7 3.9 14.8 390* E8 4.1 9.0 280 E9 3.9 15.9 320* C1 3.8 15.1 380* E10 4.0 16.9 370* C2 3.8 16.0 350* E11 3.8 17.2 380*

[0235] Tables 3 to 6 summarize further device data of OLEDs comprising the inventive compounds HTM-10 to HTM-14.

TABLE-US-00011 TABLE 3 Device Setupgreen EBL devices HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm E14 HTM: p-doped(5%) HTM HTM-10 TMM-1: TMM-2(28%):TEG(12%) ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm 30 nm 30 nm 1 nm E15 HTM: p-doped(5%) HTM HTM-11 TMM-1: TMM-2(28%):TEG(12%) ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm 30 nm 30 nm 1 nm E16 HTM: p-doped(5%) HTM HTM-12 TMM-1: TMM-2(28%):TEG(12%) ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm 30 nm 30 nm 1 nm E17 HTM: p-doped(5%) HTM HTM-13 TMM-1: TMM-2(28%):TEG(12%) ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm 30 nm 30 nm 1 nm E18 HTM: p-doped(5%) HTM HTM-14 TMM-1: TMM-2(28%):TEG(12%) ETM:LiQ(50%) LiQ 20 nm 220 nm 10 nm 30 nm 30 nm 1 nm

TABLE-US-00012 TABLE 4 Device Setupblue EBL devices HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm E19 HTM: p-doped(5%) HTM HTM-10 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E20 HTM: p-doped(5%) HTM HTM-11 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E21 HTM: p-doped(5%) HTM HTM-13 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E22 HTM: p-doped(5%) HTM HTM-14 H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm

TABLE-US-00013 TABLE 5 Device Setupblue HTL devices HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm E23 HTM-10: p-doped(5%) HTM-10 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E24 HTM-11: p-doped(5%) HTM-11 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E25 HTM-12: p-doped(5%) HTM-12 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E26 HTM-13: p-doped(5%) HTM-13 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E27 HTM-14: p-doped(5%) HTM-14 EBM H:SEB(5%) ETM:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm

TABLE-US-00014 TABLE 6 Data of the OLEDs U @ 10 EQE @ 10 LT80 @ 60/40* mA/cm.sup.2 (V) mA/cm.sup.2 (%) mA/cm.sup.2 (h) E14 4.0 15.6 360* E15 3.7 17.2 320* E16 3.7 16.7 310* E17 3.7 16.6 430* E18 3.7 16.8 380* E19 4.0 7.8 300 E20 3.6 10.2 300 E21 3.6 10.0 370 E22 3.6 9.6 400 E23 4.0 7.4 350 E24 4.4 9.1 230 E25 4.1 10.0 280 E26 4.2 9.6 270 E27 4.0 9.8 340

TABLE-US-00015 TABLE 7 Materials [00662] [00663] [00664] [00665] [00666] [00667] [00668] [00669] [00670] [00671] [00672] [00673] [00674] [00675] [00676] [00677] [00678] [00679] [00680] [00681] [00682] [00683] [00684] [00685]