MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present application relates to a spirobifluorene derivative of a specific formula (I) which is suitable for use in electronic devices.

##STR00001##

Claims

1.-14. (canceled)

15. A compound of a Formula (I) ##STR00524## where the following applies to the variables: Ar.sup.L is selected from aromatic ring systems having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3, and heteroaromatic ring systems having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3; Ar.sup.1 and Ar.sup.2 are, identically or differently, selected from aromatic ring systems having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3, and heteroaromatic ring systems having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3; E is a single bond or is a divalent group selected from C(R.sup.3).sub.2, N(R.sup.3), O, and S; R.sup.1 is, identically or differently on each occurrence, selected from F; Cl; Br; I; CN; SCN; NO.sub.2; SF.sub.5; alkyl groups; alkoxy groups; thioalkyl groups; alkenyl groups; alkynyl groups; and silyl groups which are substituted with one or more groups selected from groups R.sup.4 and alkyl groups, alkoxy groups, thioalkyl groups, alkenyl groups, and alkynyl groups; where the alkyl, alkoxy and thioalkyl groups are selected from straight-chain alkyl, alkoxy and thioalkyl groups having 1 to 20 C atoms, which may be substituted by one or more radicals R.sup.4, and branched or cyclic alkyl, alkoxy and thioalkyl groups having 3 to 20 C atoms, which may be substituted by one or more radicals R.sup.4; and where the alkenyl groups are selected from alkenyl groups having 2 to 20 C atoms, which may be substituted by one or more radicals R.sup.4; and where the alkynyl groups are selected from alkynyl groups having 2 to 20 C atoms, which may be substituted by one or more radicals R.sup.4; R.sup.2 is, identically or differently at each occurrence, selected from ##STR00525## H, D, F, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, 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.4, 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.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2; R.sup.3 is, identically or differently at each occurrence, selected from H, D, F, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, 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.3 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.4, 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.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2; R.sup.4 is, identically or differently at 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, 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 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, or 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; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by F and CN; n is on each occurrence, identically or differently, 0 or 1, where in the case of n=0, the group R.sup.1 is not present, and a group R.sup.2 is bonded instead in this position; and k is 0 or 1; where in the case of k=O, the group Ar.sup.L is not present and the nitrogen atom and the spirobifluorene group are directly connected; 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; characterized in that at least two indices n in Formula (I) are 1.

16. The compound according to claim 15, wherein index k is 0, so that the group Ar.sup.L is not present, and the spirobifluorene and the nitrogen atom of the amine are directly connected with each other.

17. The compound according to claim 15, wherein groups Ar.sup.1 and Ar.sup.2 are, identically or differently, selected from radicals derived from a group selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl and triazinyl, where the groups may each be substituted by one or more radicals R.sup.3, or from combinations of 2 or 3 radicals derived from those groups, where the groups may each be substituted by one or more radicals R.sup.3.

18. The compound according to claim 15, wherein 2, 3, or 4 indices n are equal to 1, and the rest of the indices n is equal to 0.

19. The compound according to claim 15, wherein the compound has not more than one radical R.sup.1 bonded to each aromatic six-ring of the spirobifluorene.

20. The compound according to claim 15, wherein groups R.sup.1 are selected, identically or differently on each occurrence, from straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms, which may optionally be substituted by one or more groups F, and from branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, which may optionally be substituted by one or more groups F.

21. The compound according to claim 15, wherein the groups R.sup.1 conform to one of the following formulae TABLE-US-00019 CH.sub.3 C(CH.sub.3).sub.3 CH.sub.2CH.sub.3 R.sup.1-1 R.sup.1-2 R.sup.1-3 CH.sub.2CH(CH.sub.3).sub.2 CF.sub.3 CF.sub.2CF.sub.3 R.sup.1-4 R.sup.1-5 R.sup.1-6 OCF.sub.3 SCF.sub.3 SF.sub.5 R.sup.1-7 R.sup.1-8 R.sup.1-9 OCF.sub.2CF.sub.3 SCF.sub.2CF.sub.3 R.sup.1-10 R.sup.1-11 R.sup.1-12 R.sup.1-13 R.sup.1-14 R.sup.1-15 CN SCN F R.sup.1-16 R.sup.1-17 R.sup.1-18 Cl Br I R.sup.1-19 R.sup.1-20 R.sup.1-21 OCH.sub.3 SCH.sub.3 Si(CH.sub.3).sub.3 R.sup.1-22 R.sup.1-23 R.sup.1-24 Si(CH.sub.3).sub.2(t-Bu) Si(iPr).sub.3 Si(CH.sub.3).sub.2Ph R.sup.1-25 R.sup.1-26 R.sup.1-27

22. The compound according to claim 15, wherein the compound conforms to one of Formulae (I-A-1) to (I-A-9) and (I-B-1) to (I-B-9) ##STR00530## ##STR00531## ##STR00532## ##STR00533## where the variables are defined in claim 15, and where the free positions on the spirobifluorene may be substituted with a group R.sup.2 at each occasion.

23. A process for preparation of the compound according to claim 15, which comprises the reactions steps 1) metallation of a biphenyl derivative which has a reactive group in a position which is ortho to the phenyl-phenyl bond; 2) adding the metallated biphenyl derivative to a fluorenone derivative which has a group A in its 1-position; where the group A is selected from i) X, or ii) ArX, or iii) NAr.sub.2, or iv) ArNAr.sub.2, where Ar is aromatic or heteroaromatic group, and where X is a reactive group; and 3) cyclisation of the resulting addition product to a spirobifluorene derivative under acidic conditions or with a Lewis acid.

24. An oligomer, polymer or dendrimer, comprising one or more compounds of Formula (I) according to claim 15, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any positions in Formula (I) substituted by R.sup.1, R.sup.2 or R.sup.3.

25. The formulation, comprising at least one compound of Formula (I) according to claim 15 and at least one solvent.

26. The formulation, comprising at least one polymer, oligomer or dendrimer according to claim 24, and at least one solvent.

27. An electronic device, comprising at least one compound according to claim 15, or at least one polymer, oligomer or dendrimer according to claim 24.

28. 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 according to claim 15.

Description

EXAMPLES

A) Synthesis Examples

A-1) Route 1

Synthesis of 2,7-di-tert-Butyl-1-bromospiro-9,9-bifluorene 1a

[0112] ##STR00116##

[0113] A solution of 4,4-di-t-Butyl-2,Br-biphenyl (250 g, 725 mmol) in THF (1900 ml) is treated with 318 mL of n-BuLi (2.5 M in hexane, 785 mmol) under argon at 78 C. The mixture is stirred for 30 minutes. A solution of 1-Br-fluoren-9-one (144 g, 556 mmol) in 1000 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 mixture of the alcohol (262 g, 90%), acetic acid (2200 mL) and concentrated HCl (100 mL) is refluxed for 2 hours. After cooling, the mixture is filtered and washed with water and dried under vacuum. The product is isolated in the form of a white solid (240 g, 95% of theory).

[0114] The synthesis of further brominated spirobifluorene derivatives is carried out analogously:

TABLE-US-00002 Product: Ex. Bromo-biphenyl Bromo-fluorenone Bromo-Spirobifluorene 1b [00117] [00118] [00119] 1c [00120] [00121] [00122] 1d [00123] [00124] [00125] 1e [00126] [00127] [00128] 1f [00129] [00130] [00131] 1g [00132] [00133] [00134] 1h [00135] [00136] [00137] 1i [00138] [00139] [00140] 1j [00141] [00142] [00143] 1k [00144] [00145] [00146] 1l [00147] [00148] [00149] 1m [00150] [00151] [00152]

Synthesis of 2,7-di-tert-Butyl-4-biphenyl-2-(9,9-dimethyifluorenyl)-1-spiro-9,9-bifluorenylamine 2a

[0115] ##STR00153##

[0116] Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide (16.0 g, 166 mmol) are added to a solution of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (40.0 g, 111 mmol) and 2,7-di-tertButyl-1-bromospiro-9,9-bifluorene (56.9 g, 108 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 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 ethyl acetate/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice (p=310.sup.4 mbar, T=298 C.). The product is isolated in the form of a pale-yellow solid (20.4 g, 24% of theory, purity >99.99% according to HPLC).

[0117] The following compounds are obtained analogously:

TABLE-US-00003 Ex. Br-spiro Amine Product 2b [00154] [00155] [00156] 2c [00157] [00158] [00159] 2d [00160] [00161] [00162] 2e [00163] [00164] [00165] 2f [00166] [00167] [00168] 2g [00169] [00170] [00171] 2h [00172] [00173] [00174] 2i [00175] [00176] [00177] 2j [00178] [00179] [00180] 2k [00181] [00182] [00183] 2l [00184] [00185] [00186]

A-2) Route 2: Synthesis of 2,7-di-tert-Butyl-4-biphenyl-2-(9,9-dimethyl-fluorenyl)-1-spiro-9,9-bifluorenylamine 2a

Synthesis of 1-(1-biphen-4-yl)-(9,9-dimethylfluoren-2-yl)amine-9H-Fluoren-9-one 3a

[0118] ##STR00187##

[0119] Tri-tert-butylphosphine (4.5 ml of a 1.0 M solution in toluene, 1.9 mmol), palladium acetate (217 mg, 0.97 mmol) and sodium tert-butoxide (13.9 g, 145 mmol) are added to a solution of 1-biphenyl-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine (40.0 g, 111 mmol), 1-bromo-fluoren-9-one, (25 g, 96 mmol) in degassed toluene (200 ml), and the mixture is heated under reflux overnight. 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 product is isolated in the form of a pale-yellow solid (43 g, 82% of theory).

[0120] The following compounds are obtained analogously:

TABLE-US-00004 Bromo- Product: Ex. fluorenone Amine 1-Amine-fluorenone 3b [00188] [00189] [00190] 3c [00191] [00192] [00193] 3d [00194] [00195] [00196] 3e [00197] [00198] [00199] 3f [00200] [00201] [00202] 3g [00203] [00204] [00205] 3h [00206] [00207] [00208] 3i [00209] [00210] [00211] 3j [00212] [00213] [00214] 3k [00215] [00216] [00217] 3l [00218] [00219] [00220] 3m [00221] [00222] [00223]

Synthesis of 2,7-di-tert-Butyl-4-biphenyl-2-(9,9-dimethylfluorenyl)-1-spiro-9,9-bifluorenylamine 4a

[0121] ##STR00224##

[0122] A solution of 4,4-di-t-butyl-2-Br-biphenyl (17 g, 49 mmol) in THF (90 ml) is treated with 25 mL of n-BuLi (2.1 M in hexane, 50 mmol) under argon at 78 C. The mixture is stirred for 30 minutes. A solution of 1-(1-biphen-4-yl)-(9,9-dimethylfluoren-2-yl)amine-9H-fluoren-9-one (27 g, 50 mmol) in 90 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 extracted with ethyl acetate. The intermediate alcohol is obtained after the solvent is removed (31 g, 76%). Without further purification, a mixture of the alcohol, acetic acid (700 mL) and concentrated HCl (62 mL) is refluxed for 2 hours. After cooling, the mixture is filtered and washed with water. The residue is crystallised from toluene. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo. The product is isolated in the form of a pale-yellow solid (13 g, 42% of theory, purity >99.99% according to HPLC).

[0123] The following compounds are obtained analogously:

TABLE-US-00005 Ex. 1-Amine-fluorenone Br-Biphenyl 4b [00225] [00226] 4c [00227] [00228] 4d [00229] [00230] 4e [00231] [00232] 4f [00233] [00234] 4g [00235] [00236] 4h [00237] [00238] 4i [00239] [00240] 4j [00241] [00242] 4k [00243] [00244] 4l [00245] [00246] 4m [00247] [00248] Ex. Product: 4b [00249] 4c [00250] 4d [00251] 4e [00252] 4f [00253] 4g [00254] 4h [00255] 4i [00256] 4j [00257] 4k [00258] 4l [00259] 4m [00260]

A-3) Route 3: Synthesis of 2,7-di-tert-Butyl-biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[1-(9,9-spiro-bifluoren-4-yl)-phenyl]-amine

Synthesis of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]-amine

[0124] ##STR00261##

[0125] 102 g (198 mmol) of Biphenyl-4-yl-(4-bromo-phenyl)-(9,9-dimethyl-9H-fluoren-2-yl)-amine, 4.8 g (5.9 mmol) of Pd(dppf)Cl.sub.2, 61.6 g (238 mmol) of bis(pinacolato)diboron and 58.3 g (594 mmol) of potassium acetate are dissolved in 1300 mL of 1,4-dioxane. 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 a pale-yellow solid (87 g, 78% of theory).

Synthesis of 2,7-di-tert-Butyl-biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[1-(9,9-spiro-bifluoren-4-yl)-phenyl]-amine 5a

[0126] ##STR00262##

[0127] 28 g (49.4 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, 20 g (39 mmol) of 2,7-di-tert-butyl-1-bromospiro-9,9-bifluorene, 1.8 g (2.5 mmol) of PdCl.sub.2(Cy).sub.3, 15 g (99 mmol) of cesium fluoride are dissolved in 500 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.

[0128] The product is isolated in the form of a pale-yellow solid (9 g, 25% of theory, purity >99.99% according to HPLC).

[0129] The following compounds are synthesized analogously:

TABLE-US-00006 Ex. Br-Spiro Amine 5b [00263] [00264] 5c [00265] [00266] 5d [00267] [00268] 5e [00269] [00270] Ex. Product 5b [00271] 5c [00272] 5d [00273] 5e [00274]

A-4) Route 4: Synthesis of 2,7-di-tert-Butyl-9-Spiro-1-yl-3,6-diphenyl-9H-carbazol 6a

[0130] ##STR00275##

[0131] 19.2 g (38 mmol) 2,7-di-tert-Butyl-1-bromospiro-9,9-bifluorene, 15 g (47 mmol) 3,6-Diphenyl-9-H-carbazole and 29.2 g Rb.sub.2CO.sub.3 are suspended in 250 mL p-Xylol. To the suspension are given 0.95 g (4.2 mmol) Pd(OAc).sub.2 and 12.6 ml of a 1M solution of Tri-tert-butylphosphine. The mixture is stirred 24 h under reflux. After cooling the organic phase is separated, washed three times with 150 mL water and is subsequently concentrated to dryness in vacuo. The residue is hot extracted with toluene, recrystallized three times from toluene and subsequently sublimated at high vacuum. Yield is 19.6 g (26.2 mmol) corresponding to 68% of theory. Purity is according to HPLC 99.9%.

[0132] The following compounds are obtained analogously:

TABLE-US-00007 Starting material 1 Starting material 2 6b [00276] [00277] 6c [00278] [00279] 6d [00280] [00281] 6e [00282] [00283] Product 6b [00284] 6c [00285] 6d [00286] 6e [00287]

A-5) Route 5: Synthesis of Compound 7a

Synthesis of 1-(4-Chloro-phenyl)-fluoren-9-one 7a

[0133] ##STR00288##

[0134] 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 crystallization with MeOH. Yield: 125 g (420 mmol), 90% of theory, purity according to HPLC >98%.

TABLE-US-00008 1-Br-Fluorenone Boron acid Product 7b [00289] [00290] [00291] 7c [00292] [00293] [00294] 7d [00295] [00296] [00297] 7e [00298] [00299] [00300] 7f [00301] [00302] [00303]

Synthesis of 1-(4-Brom-phenyl)-fluoren-9-one 1-1 (8a)

[0135] ##STR00304##

Synthesis of boronester

[0136] 10 g (39 mmol) of 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 8a

[0137] 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 crystallisation with MeOH. Yield: 19 g (54 mmol), 78% of theory, purity according to HPLC >98%.

[0138] The following compounds are prepared analogously:

TABLE-US-00009 8b [00305] [00306] [00307] [00308] 8c [00309] [00310] [00311] [00312] 8d [00313] [00314] [00315] [00316] 8e [00317] [00318] [00319] [00320] 8f [00321] [00322] [00323] [00324]

Synthesis of 1-(4-((1,1-biphenyl-4-yl)-(9,9-dimethyl-9H-fluoren-2-yl)amino)phenyl)-9H-Fluoren-9-one 9a

[0139] ##STR00325##

[0140] Tri-tert-butylphosphine (4.5 ml of a 1.0 M solution in toluene, 1.9 mmol) and 0.98 g (1 mmol) of Pd.sub.2(dba).sub.3 and sodium tert-butoxide (5.1 g, 50 mmol) are added to a solution of 1-biphenyl-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (32 g, 90 mmol), 1-1-(4-chlor-phenyl)-fluoren-9-one, (25 g, 86 mmol) in degassed toluene (200 ml), and the mixture is heated under reflux overnight. 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 product is isolated in the form of a pale-yellow solid (43 g, 81% of theory).

TABLE-US-00010 Ex. Fluorenone Amine 9b [00326] [00327] 9c [00328] [00329] 9d [00330] [00331] 9e [00332] [00333] 9f [00334] [00335] 9g [00336] [00337] 9h [00338] [00339] 9i [00340] [00341] 9j [00342] [00343] 9k [00344] [00345] 9l [00346] [00347] Ex. Product: 1-Amine-fluorenone 9b [00348] 9c [00349] 9d [00350] 9e [00351] 9f [00352] 9g [00353] 9h [00354] 9i [00355] 9j [00356] 9k [00357] 9l [00358]

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 10a

[0141] ##STR00359##

[0142] A solution of 4,4-di-t-Butyl-2,Br-biphenyl (17 g, 49 mmol) in THF (90 ml) is treated with 25 mL of n-BuLi (2.1 M in hexane, 50 mmol) under argon at 78 C. The mixture is stirred for 30 minutes. A solution of 1-(4-((1,1-biphenyl-4-yl)-(9,9-dimethyl-9H-fluoren-2-yl)amino)phenyl)-9H-Fluoren-9-one (27 g, 44 mmol) in 90 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 extracted with ethyl acetate. The intermediate alcohol is obtained after the solvent is removed (31 g, 76%). Without further purification, a mixture of the alcohol, acetic acid (700 mL) and concentrated HCl (62 mL) is refluxed for 2 hours. After cooling, the mixture is filtered and washed with water. The residue is crystallised from toluene. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo. The product is isolated in the form of a pale-yellow solid (13 g, 34% of theory, purity >99.99% according to HPLC).

[0143] The following compounds are prepared analogously:

TABLE-US-00011 Ex. Product: 1-Amine-fluorenone Br-Biphenyl 10b [00360] [00361] 10c [00362] [00363] 10d [00364] [00365] 10e [00366] [00367] 10f [00368] [00369] 10g [00370] [00371] 10h [00372] [00373] 10i [00374] [00375] 10j [00376] [00377] 10k [00378] [00379] 10l [00380] [00381] 10m [00382] [00383] Ex. Product: 10b [00384] 10c [00385] 10d [00386] 10e [00387] 10f [00388] 10g [00389] 10h [00390] 10i [00391] 10j [00392] 10k [00393] 10l [00394] 10m [00395]

A-6) Route 6

Synthesis of 2,7-di-tert-butyl-8-(4-chlorophenyl)9,9-spirobifluorene 11a

[0144] ##STR00396##

[0145] 20 g (58 mmol) of 2-Br-4,4-di-tert-Butyl-1,1-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 (58 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), 53%; purity approx. 98% according to .sup.1H-NMR.

[0146] The following compounds are synthesized analogously:

TABLE-US-00012 Example Reagent 1 Reagent 2 11b [00397] [00398] 11c [00399] [00400] 11d [00401] [00402] 11e [00403] [00404] 11f [00405] [00406] 11g [00407] [00408] 11h [00409] [00410] Example Product 11b [00411] 11c [00412] 11d [00413] 11e [00414] 11f [00415] 11g [00416] 11h [00417]

Synthesis of 2,7-di-tert-butyl-8-(4-chlorophenyl)-9,9-spirobifluorene 12a

[0147] ##STR00418##

[0148] 10.7 g (69 mmol) of 4-chlorophenylboronic acid, 35 g (69 mmol) of 2,7-di-tert-butyl-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 crystallisation with MeOH. Yield: 29 g (65 mmol), 94% of theory, purity according to HPLC >98%.

TABLE-US-00013 Example Reagent 1 Reagent 2 12b [00419] [00420] 12c [00421] [00422] 12d [00423] [00424] 12e [00425] [00426] 12f [00427] [00428] 12g [00429] [00430] 12h [00431] [00432] Example Product 12b [00433] 12c [00434] 12d [00435] 12e [00436] 12f [00437] 12g [00438] 12h [00439]

Synthesis of 2,7-di-tert-butyl-8-(4-chlorophenyl)-9,9-spirobifluorene

[0149] ##STR00440##

Synthesis of 2-{2,7-di-tert-butyl-9,9-spirobi[fluorene]-8-yl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ester 13a

[0150] ##STR00441##

[0151] 50 g (99 mmol) of 2,7-di-tert-butyl-1-brom-spirofluorene, 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).

[0152] The following compounds are prepared analogously:

TABLE-US-00014 Example Reagent 1 Product 13b [00442] [00443] 13c [00444] [00445] 13d [00446] [00447] 13e [00448] [00449]

Synthesis of 2-{2,7-di-tert-butyl-9,9-spirobi[fluorene]-8-yl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ester 14a

[0153] ##STR00450##

[0154] 50 g (93 mmol) of 2,7-di-tert-butyl-1-brom-spirofluorene are initially introduced in 50 ml of THF at 20 C. 56 ml of BuLi (2 M in hexane) are added dropwise at this temperature. After 4 hours, 18.6 g (100 mmol) of isopropoxytetramethyldioxaborolane 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 (79 mmol), 85% of theory, purity according to HPLC >98%.

[0155] The following compounds are prepared analogously:

TABLE-US-00015 Example Reagent 1 Reagent 2 14b [00451] [00452] 14c [00453] [00454] 14d [00455] [00456] 14e [00457] [00458] Example Product 14b [00459] 14c [00460] 14d [00461] 14e [00462]

Synthesis of 2,7-di-tert-butyl-8-(4-chlorophenyl)-9,9-spirobifluorene 15a

[0156] ##STR00463##

[0157] 20.3 g (37 mmol) of 2-{2,7-di-tert-butyl-9,9-spirobi[fluorene]-8-yl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ester 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 (78% of theory).

[0158] The following compounds are prepared analogously:

TABLE-US-00016 Example Reagent 1 Reagent 2 15b [00464] [00465] 15c [00466] [00467] 15d [00468] [00469] 15e [00470] [00471] 15f [00472] [00473] Example Product 15b [00474] 15c [00475] 15d [00476] 15e [00477] 15f [00478]

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 16a

[0159] ##STR00479##

[0160] 10.1 g (28 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine and 14.5 g (27 mol) of the 2,7-di-tert-butyl-8-(4-chlorophenyl)-9,9-spirobifluorene 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 (48% of theory).

[0161] The following compounds are also prepared analogously to the synthesis of compound 1.

TABLE-US-00017 Ex. Starting material 1 Starting material 2 16b [00480] [00481] 16c [00482] [00483] 16d [00484] [00485] 16e [00486] [00487] 16f [00488] [00489] 16g [00490] [00491] 16h [00492] [00493] 16i [00494] [00495] 16j [00496] [00497] 16k [00498] [00499] 16l [00500] [00501] Ex. Product 16b [00502] 16c [00503] 16d [00504] 16e [00505] 16f [00506] 16g [00507] 16h [00508] 16i [00509] 16j [00510] 16k [00511] 16l [00512]

B) Use Examples

[0162] 1) EBL Use of Compounds

[0163] A fluorescent blue emitting OLED comprising the compound HTM according to the present application in the EBL is prepared. The OLED has the following stack structure:

Anode/HIM:F4TCNQ (5%) (20 nm)/HIM (180 nm)/HTM (10 nm)/H:SEB (5%) (20 nm)/ETM:LiQ (50%) (30 nm)/LiQ (1 nm)/cathode.

[0164] In the above stack, the anode consists of a glass plate coated with a 50 nm layer of structured ITO. The cathode is made of a 100 nm thick layer of Al. The structures of the materials which are present in the different layers are given in Table 1. The materials are deposited by thermal vapor deposition in a vacuum chamber. If two materials are present in a layer, the percentage given above is the proportion of the second material in percent by volume.

[0165] The OLED is electrically driven, and is characterized by establishing the following parameters: 1) external quantum efficiency (EQE, measured in percent) is determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, at a current density of 10 mA/cm.sup.2; 2) lifetime LD80 @ 5000 cd/m.sup.2, which is the time until the OLED has dropped from its starting brightness of 5000 cd/m.sup.2 to 80% of its starting brightness; 3) operating voltage at 10 mA/cm.sup.2, and 4) LD80 @ 60 mA/cm.sup.2, which is the time until the OLED has dropped from its starting brightness at 60 mA/cm.sup.2 to 80% of its starting brightness.

[0166] For the OLED, the following values are measured: EQE @ 10 mA/cm.sup.2: 7.6%, lifetime LD80 @ 5000 cd/m.sup.2: 320 h, operating voltage at 10 mA/cm.sup.2: 4.0 V.

[0167] Compounds 2a-2c, 2e-21, 4a-4m, 5a-5e, 6a-6e, 10a-10m and 16a-161 of the synthesis examples give results which are similar to the ones obtained with compound HTM.

[0168] 2) HTL Use of Compounds

[0169] A fluorescent blue emitting OLED comprising the compound HTM-1 according to the present application in the HIL and the HTL is prepared. The OLED has the following stack structure:

Anode I/HTM-1:F4TCNQ (5%) (20 nm) I/HTM-1 (180 nm) I/EBM (10 nm) I/H:SEB (5%) (20 nm) I/ETM:LiQ (50%) (30 nm) I/LiQ (1 nm) I cathode.

[0170] The preparation of the OLED and of the electrode layers, and the characterization is the same as described above in 1).

[0171] For the OLED, the following values are measured: EQE @ 10 mA/cm.sup.2: 8.2%, lifetime LD80 @ 60 mA/cm.sup.2: 340 h, operating voltage at 10 mA/cm.sup.2: 4.2 V.

[0172] Compounds 2a-21, 4a-4f, 4h-4m, 5a-5e, 6a-6e, 10a-10m and 16a-161 of the synthesis examples give results which are similar to the ones obtained with compound HTM-1.

[0173] 3) Comparison of Compound EBM-1 According to the Application with Compound EBM-2

[0174] OLEDs are prepared which have the following stack structure:

[0175] Example according to the invention:

Anode I/HIM:F4TCNQ (5%) (20 nm)/HIM (180 nm)/EBM-1 (10 nm)/H:SEB (5%) (20 nm) I/ETM:LiQ (50%) (30 nm) I/LiQ (1 nm) I cathode.

COMPARATIVE EXAMPLE

[0176] As above, only EBM-1 is replaced by EBM-2.

[0177] The preparation of the OLEDs and of the electrode layers, and the characterization is the same as described above in 1).

[0178] For the OLED comprising the compound EBM-1, the following values are measured: EQE @ 10 mA/cm.sup.2: 8.2%, lifetime LD80 @ 60 mA/cm.sup.2: 103 h, operating voltage at 10 mA/cm.sup.2: 4.3 V.

[0179] For the OLED comprising the compound EBM-2 (comparative example), the following values are measured: EQE @ 10 mA/cm.sup.2: 8.1%, lifetime LD80 @ 60 mA/cm.sup.2: 81 h, operating voltage at 10 mA/cm.sup.2: 4.1 V.

[0180] This shows in a direct comparison of performance, that an OLED comprising the compound EBM-1 according to the present application, shows strongly improved lifetime, compared to an OLED comprising the compound EBM-2 (comparative example). The other parameters efficiency and operating voltage remain similar.

TABLE-US-00018 TABLE 1 Chemical structures of compounds [00513] F4TCNQ [00514] HIM [00515] H [00516] SEB [00517] ETM [00518] LiQ [00519] HTM [00520] HTM-1 [00521] EBM [00522] EBM-1 [00523] EBM-2