HEXAMETHYLINDANES

Abstract

The present invention relates inter alia to organic compounds, compositions, formulations and electronic devices.

Claims

1.-20. (canceled)

21. A compound according to the formula (1), ##STR00448## wherein: Y is at each occurrence same or different and selected from C(R.sup.1).sub.2,N(R.sup.1), C(O), C(S), O, or S; X is at each occurrence same or different, and X includes CR.sup.1 or N; R.sup.1 is at each occurrence same or different, and R.sup.1 includes H, D, F, Cl, Br, I, CHO, N(Ar.sup.1).sub.2, C(O)Ar.sup.1, P(O)(Ar.sup.1).sub.2, S(O)Ar.sup.1, S(O).sub.2Ar.sup.1, CR.sup.2CR.sup.2Ar.sup.1, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, B(R.sup.2).sub.2, B(N(R.sup.2).sub.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more R.sup.2, wherein one or more non-adjacent methylene groups may be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, CNR.sup.2, P(O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S, or C(O)NR.sup.2, and wherein one or more hydrogen atoms can include a substitution selected from D, F, Cl, Br, I, CN, NO.sub.2, or 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.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; wherein two or more substituents R.sup.1 together with the atoms to which they are bonded, or two substituents R.sup.1, together with the atom to which they are bonded, may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.2 is at each occurrence same or different, and R.sup.2 includes H, D, F, Cl, Br, I, N(R.sup.3).sub.2, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, C(O)R.sup.3, P(O)(R.sup.3).sub.2, S(O)R.sup.3, S(O).sub.2R.sup.3, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.3, where one or more non-adjacent CH.sub.2 groups is optionally 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, CNR.sup.3, P(O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or 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, or an aryloxy, aralkoxy, or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or a diarylamino group, a diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or a combination of two or more of these groups, wherein two or more substituents R.sup.2 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.3 is at each occurrence same or different, and R.sup.3 includes H, D, F, or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein on or more H atoms can be substituted for F, wherein two or more substituents R.sup.3 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.4 is at each occurrence same or different, and R.sup.4 includes Ar.sup.1, a first moiety comprising a C.sub.1-C.sub.40 alkyl, a C.sub.1-C.sub.40 unsaturated group, a C.sub.3-C.sub.40 cyclic alkyl, or a C.sub.3-C.sub.40 unsaturated cyclic group, the moiety further comprising R.sup.2, wherein one or more methylene groups, can include a substitution selected from R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, CNR.sup.2, P(O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, or C(O)NR.sup.2, wherein one or more hydrogen atoms can include a substitution selected from D, F, Cl, Br, I, CN, NO.sub.2, or Ar.sup.1; Ar.sup.1 is at each occurrence same or different, and Ar.sup.1 includes an aromatic ring, an aromatic ring system, a hetero-aromatic ring, a hetero-aromatic ring system, or an aromatic hetero-aromatic ring system, wherein Ar.sup.1 can include one or more R.sup.3 substitution; m is 0, 1 or 2; n is 0 or 1.

22. The compound according to claim 21, wherein R.sup.4 includes an aromatic or hetero-aromatic system having 5 to 60 aromatic ring atoms comprising one or more substitution R.sup.2.

23. The compound according to claim 21, wherein the compound is of the formula 1a, 1b, or 1c: ##STR00449##

24. The compound according to claim 21 wherein the compound is of the formula 2a, 2b, or 2c: ##STR00450##

25. The compound according to claim 21 wherein the compound is of the formula 3a, 3b or 3c: ##STR00451##

26. The compound according to claim 21, wherein R.sup.4 is a phenyl-, biphenyl-, terphenyl-, quarterphenyl-, pyridyl-, pyrimidinyl-, pyrazinyl-, pyridazinyl-, triazinyl-, diarylaminopenyl- or diarylaminobiphenyl group which can be substituted with one or more R.sup.2 that can be same or different in each occurrence.

27. The compound according to claim 21, wherein R.sup.4 includes one of the following groups: ##STR00452## wherein R.sup.5 is at each occurrence same or different, and R.sup.5 includes H, D, F, Cl, Br, I, CHO, N(Ar.sup.2).sub.2, C(O)Ar.sup.2, P(O)(Ar.sup.2).sub.2, S(O)Ar.sup.2, S(O).sub.2Ar.sup.2, CR.sup.6CR.sup.6Ar.sup.2, CN, NO.sub.2, Si(R.sup.6).sub.3, B(OR.sup.6).sub.2, B(R.sup.6).sub.2, B(N(R.sup.6).sub.2).sub.2, OSO.sub.2R.sup.6, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more R.sup.6, wherein one or more non-adjacent methylene groups may be replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, CO, CS, CSe, CNR.sup.6, P(O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S, or C(O)NR.sup.6, and wherein one or more hydrogen atoms can include a substitution selected from D, F, Cl, Br, I, CN, NO.sub.2, or 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.6, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6, or a combination of these systems; wherein two or more substituents R.sup.5 together with the atoms to which they are bonded, or two substituents R.sup.5, together with the atom to which they are bonded, may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.6 is at each occurrence same or different, and R.sup.6 includes H, D, F, or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein on or more H atoms can be substituted for F, wherein two or more substituents R.sup.6 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; Ar.sup.2 is at each occurrence same or different, and Ar.sup.2 includes an aromatic ring, an aromatic ring system, a hetero-aromatic ring, a hetero-aromatic ring system, or an aromatic hetero-aromatic ring system, wherein Ar.sup.2 can include 5 to 40 ring atoms, wherein Ar.sup.2 includes one or more R.sup.6 substitution; and p is 0, 1,2,3, 4 or 5.

28. A composition comprising at least one compound according to claim 21 and at least one functional material selected from the group consisting of a hole injection material (HIM), hole transport material (HTM), hole blocking material (HBM), electron injection material (EIM), electron transport material (ETM), electron blocking material (EBM), host material, matrix material, wide band gap material, fluorescent emitter, phosphorescent emitter, n-dopant and p-dopant.

29. The composition according to claim 28, wherein the functional material is a matrix material.

30. The composition according to claim 28, further comprising at least one phosphorescent emitter.

31. The composition according to claim 28, further comprising at least one wide band gap material, wherein the wide band gap material.

32. The composition according to claim 28 wherein the at least one compound is covalently bonded to the oligomer, the dendrimer, or the polymer

33. A formulation comprising at least one compound according to claim 21 and at least one solvent.

34. An electronic device comprising the compound according to claim 21.

35. The electronic device according to claim 34, wherein the device is selected from the group consisting of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors and organic photoreceptors.

36. The electronic device according to claim 35, wherein the device is an electroluminescent device selected from the group consisting of organic light emitting transistors (OLETs), organic field quenching devices (OFQDs), organic light emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-Laser) and organic light emitting diodes (OLEDs).

37. The electronic device according to claim 35 for use in medicine for phototherapy.

38. The electronic device to claim 35 for cosmetic use for irradiation of human and animal skin.

39. A method for preparing the electronic device according to claim 35, the method including depositing at least one organic layer of the device by vapor deposition or from solution.

Description

WORKING EXAMPLES

Example 1

Synthesis of 1,1,2,2,3,3-Hexamethyl-1,2,3,9-tetrahydro-9-aza-cyclopenta[b]fluorene (4a) and 1,1,2,2,3,3-Hexamethyl-1,2,3,6-tetrahydro-cyclopenta[c]carbazole (5a)

[0096] ##STR00106##

Synthesis of (2-Chloro-phenyl)-(1,1,2,2,3,3-hexamethyl-indan-5-yl)-amine (3a)

[0097] In a 2 L four-necked flask 51.5 g (183 mmol, 1.0 eq) of 5-bromo-2,3-dihydro-1,1,2,2,3,3-hexamethyl-1H-Indene [1562418-80-7] are dissolved together with 25.0 g (196 mmol, 1.07 eq) 2-chloroanilin and 45.7 g (476 mmol, 2.6 eq) sodium-tert-butoxide in 840 ml of dried toluene. The mixture was degassed for 30 minutes and then, 411 mg (1.83 mmol, 0.01 eq) of palladium(II)-acetate and 1.01 g (1.83 mmol, 0.01 eq) 1,1-bis(diphenylphosphino)ferrocene are added. The reaction is heated to 100 C. for 4 hours. After the reaction is finished, 300 ml water are added and the mixture is stirred for additional 30 minutes. Then, the aqueous phase is separated and the organic phase is washed 3 times with water. The combined aqueous layers are extracted once with toluene. The combined organic layers are dried over sodium sulfate and the solvent is removed in vacuo. 54.0 g (164 mmol, 90%) of desired secondary amine 3a is obtained as brownish oil.

Synthesis of 1,1,2,2,3,3-Hexamethyl-1,2,3,9-tetrahydro-9-aza-cyclopenta[b]fluorene (4a) and 1,1,2,2,3,3-Hexamethyl-1,2,3,6-tetrahydro-cyclopenta[c]carbazole (5a)

[0098] A 1 L four-necked flask is charged with 54.0 g (164 mmol, 1.0 eq) of (2-Chloro-phenyl)-(1,1,2,2,3,3-hexamethyl-indan-5-yl)-amine 3a, 56.7 g (410 mmol, 2.5 eq) potassium carbonate and 650 ml of 1-methyl-2-pyrrolidon. After the mixture is degassed for 30 minutes, 5.03 g (49.2 mmol, 0.30 eq) pivalic acid, 736 mg (3.3 mmol, 0.02 eq) palladium(II)-acetate and 6.6 ml (6.6 mmol, 0.04 eq) of a 1 mol/l tri-tert.-butylphoshine solution in toluene is added. The reaction is stirred overnight at 130 C. and after the reaction is finished, the solvent and the pivalic acid are removed in vacuo and the remaining solid is dissolved in 100 ml toluene. The solution is washed 3 times with 150 ml water and dried over sodium sulfate. After evaporation of the solvent, the isomeric mixture is separated by two-fold crystallization from n-heptane. 13.4 g (45.9 mmol, 28%) of isomer 4a are obtained as light-brown crystals and 29.1 g (100 mmol, 61%) of isomer 5a are obtained after evaporation of the solvent.

Synthesis of 1,1,2,2,3,3-Hexamethyl-5-(2-nitro-phenyl)-indan (8a)

[0099] 50.0 g (152 mmol, 1.0 eq) 2-(1,1,2,2,3,3-Hexamethyl-indan-5-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaboro-lane and 32.3 g (160 mmol, 1.05 eq) 1-bromo-2-nitrobenze are dissolved together with 32.3 g (305 mmol, 2.0 eq) sodium carbonate in 400 ml toluene, 400 ml 1,4-dioxane and 200 ml water. After degassing for 30 minutes, 1.76 g (1.52 mmol, 0.01 eq) tetrakis(triphenyl-phosphin)palladium(0) are added and the mixture is stirred overnight at reflux. Then, the phases are separated and the aqueous phase is extracted once with toluene. The combined organic layers are washed with sat. NaCl solution and dried over sodium sulfate. After crystallization from n-heptane, 28.0 g (86 mmol, 57%) 8a are obtained as slight brown crystals. The remaining solution is evaporated until more product precipitated and 18.6 g (57 mmol, 38%) of additional product 8a are obtained.

Synthesis of 1,1,2,2,3,3-Hexamethyl-1,2,3,9-tetrahydro-9-aza-cyclopenta[b]fluorene (4a) and 1,1,2,2,3,3-Hexamethyl-1,2,3,6-tetrahydro-cyclopenta[c]carbazole (5b)

[0100] 40.5 g (124 mmol, 1.0 eq) 8a are reacted with 417 mg (2.5 mmol, 0.02 eq) palladium(II)-acetate and 2.40 g (13 mmol, 0.11 eq) 1,10-phenanthrolin in 500 ml DMF in the presence of 2.8 l carbon monoxide in an autoclave (140 C., max. 7.6 bar, 35 h). After the reaction is finished, the mixture is filtered with 95:5 heptane/THF over silica and the solvents are evaporated in vacuo. The isomeric mixture is separated by crystallization. 14.3 g (49 mmool, 40%) of isomer 4a are obtained after two crystallizations as light-brownish crystals, whereas 19.7 g (67 mmol, 55%) of isomer 5a are obtained after evaporation of the solvent.

Example 2

Synthesis of 6-Bromo-1,1,2,2,3,3-hexamethyl-1,2,3,9-tetrahydro-9-aza-cyclopenta[b]fluorene (9a)

[0101] ##STR00107##

[0102] 15.1 g (51.8 mmol, 1.0 eq) carbazole 4a is dissolved in 400 ml THF and cooled in an ethanol/ice bath. Then, 9.51 g (53.4 g, 1.03 eq) N-bromsuccinimide are added subsequently at 0-5 C. After stirring for one hour at this temperature the reaction is stirred overnight at room temperature. The mixture is concentrated to about 50 ml and 100 ml water are added. The precipitate is filtered and washed with water. 18.9 g (51.0 mmol, 99%) of a slightly brown solid are obtained.

[0103] Analogously the following compound can be obtained:

TABLE-US-00001 Compound Educt Product Yield [%] 9b [00108] [00109] 43

Example 3

Synthesis of 7-(1,1,2,2,3,3-Hexamethyl-1,2,3,9-tetrahydro-9-aza-cyclopenta[b]fluoren-6-yl)-12,12-dimethyl-10-phenyl-10,12-dihydro-10-aza-indeno[2,1-b]fluorene (11a)

[0104] 13.0 g (35.1 mmol, 1.0 eq) of 6-Bromo-1,1,2,2,3,3-hexamethyl-1,2,3,9-tetrahydro-9-aza-cyclopenta[b]fluorene 9a, 17.5 g (36.2 mmol, 1.03 eq) 12,12-Dimethyl-10-phenyl-7-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-10,12-dihydro-10-aza-indeno[2,1-b]fluorine [1379585-25-7] 10a and 18.6 g (70.2 mmol, 2.0 eq) potassium phosphate are dissolved in 200 ml toluene, 200 ml 1,4-dioxane and 100 ml water. After the mixture is degassed for 30 minutes, 79 mg (0.35 mmol, 0.01 eq) palladium(II)-acetate and 427 mg (1.40 mmol, 0.04 eq) tri(o-tolyl)-phosphine are added. The reaction is stirred at reflux overnight and warmed to room temperature. The mixture is filtered over Celite and diluted with 400 ml toluene. The aqueous layer is separated, the organic phase washed three times with NaCl solution and the combined organic phases dried over sodium sulfate. After evaporation of the solvent, the residue is stirred for 30 minutes in 200 ml n-heptane at 60 C. After filtration 21.3 g (32.8 mmol, 93%) of product 11a are obtained as grey-brown solid.

[0105] Analogously the following compounds can be obtained:

TABLE-US-00002 Yield Comp. Educt Educt Product [%] 11b [00110] [00111] [00112] 89 11c [00113] [00114] [00115] 92 11d [00116] [00117] [00118] 74 11e [00119] [00120] [00121] 82 11f [00122] [00123] [00124] 91 11g [00125] [00126] [00127] 82 11h [00128] [00129] [00130] 96 11i [00131] [00132] [00133] 84 11j [00134] [00135] [00136] 55 11k [00137] [00138] [00139] 78 11l [00140] [00141] [00142] 96 11m [00143] [00144] [00145] 86 11n [00146] [00147] [00148] 71 11o [00149] [00150] [00151] 32 11p [00152] [00153] [00154] 56 11q [00155] [00156] [00157] 79 11r [00158] [00159] [00160] 87 11s [00161] [00162] [00163] 72 11t [00164] [00165] [00166] 83 11u [00167] [00168] [00169] 84 11v [00170] [00171] [00172] 46 11w [00173] [00174] [00175] 88 11x [00176] [00177] [00178] 86 11y [00179] [00180] [00181] 63 11z [00182] [00183] [00184] 51 11aa [00185] [00186] [00187] 68 11ab [00188] [00189] [00190] 94 11ac [00191] [00192] [00193] 69 11ad [00194] [00195] [00196] 95 11ae [00197] [00198] [00199] 76 11af [00200] [00201] [00202] 82 11ag [00203] [00204] [00205] 87 11ah [00206] [00207] [00208] 91 11ai [00209] [00210] [00211] 94 11aj [00212] [00213] [00214] 85 11ak [00215] [00216] [00217] 83 11al [00218] [00219] [00220] 76

Example 4

Synthesis of 7-(1,1,2,2,3,3-Hexamethyl-9-phenyl-1,2,3,9-tetrahydro-9-aza-cyclopenta[b]fluoren-6-yl)-12,12-dimethyl-10-phenyl-10,12-dihydro-10-aza-indeno[2,1-b]fluorene (13a)

[0106] 20.0 g (30.8 mmol, 1.0 eq) 7-(1,1,2,2,3,3-Hexamethyl-1,2,3,9-tetrahydro-9-aza-cyclopenta[b]fluoren-6-yl)-12,12-dimethyl-10-phenyl-10,12-dihydro-10-aza-indeno[2,1-b]fluorene 11a, 3.57 ml (33.9 mmol, 1.10 eq) bromobenzene and 8.88 g (92.5 mmol, 3.0 eq) sodium-tert-butoxide are dissolved in 500 ml dry toluene. After degassing for 30 minutes, 138 mg (0.616 mmol, 0.02 eq) palladium(II)-acetate and 1.23 ml (1.23 mmol, 0.04 eq) of a tri-tert-butylphosphine solution (1 mol/l in toluene) are added. The reaction is stirred for two days at reflux, cooled to room temperature and filtered over Celite. The filtrate is concentrated to about 50 ml and 500 ml heptane are added. The mixture is stirred for one hour and the precipitate filtered and dried. 18.6 g (25.7 mmol, 83%) of a grey solid are obtained as crude product. The product is purified by hot extraction with heptane/toluene 5:1 and three times recrystallized with toluene/acetonitrile. After two sublimations 2.45 g (3.38 mmol, 11%) of final product 13a are obtained as a colorless solid in a purity >99.9% (HPLC).

[0107] Analogously the following compounds can be obtained:

TABLE-US-00003 Yield Comp. Educt Educt Product [%] 13b [00221] [00222] [00223] 43 [591-50-4] 13c [00224] [00225] [00226] 56 [591-50-4] 13d [00227] [00228] [00229] 23 [92-66-0] 13e [00230] [00231] [00232] 44 [2113-57-7] 13f [00233] [00234] [00235] 38 [2113-57-7 13g [00236] [00237] [00238] 59 [591-50-4] 13h [00239] [00240] [00241] 21 [591-50-4] 13i [00242] [00243] [00244] 17 [591-50-4] 13j [00245] [00246] [00247] 45 [591-50-4] 13k [00248] [00249] [00250] 19 [591-50-4] 13l [00251] [00252] [00253] 54 [591-50-4] 13m [00254] [00255] [00256] 61 [591-50-4] 13n [00257] [00258] [00259] 15 [591-50-4] 13o [00260] [00261] [00262] 24 [591-50-4] 13p [00263] [00264] [00265] 33 [591-50-4] 13q [00266] [00267] [00268] 38 [591-50-4] 13r [00269] [00270] [00271] 41 [591-50-4] 13s [00272] [00273] [00274] 21 [591-50-4] 13t [00275] [00276] [00277] 18 [591-50-4] 13u [00278] [00279] [00280] 53 [591-50-4] 13v [00281] [00282] [00283] 27 [591-50-4] 13w [00284] [00285] [00286] 36 [591-50-4] 13x [00287] [00288] [00289] 19 [591-50-4] 13y [00290] [00291] [00292] 53 [591-50-4] 13z [00293] [00294] [00295] 23 [611-33-6] 13aa [00296] [00297] [00298] 65 [591-50-4] 13ab [00299] [00300] [00301] 34 [591-50-4] 13ac [00302] [00303] [00304] 71 [2113-57-7 13ad [00305] [00306] [00307] 59 [591-50-4] 13ae [00308] [00309] [00310] 35 [591-50-4] 13af [00311] [00312] [00313] 42 [103068-20-8] 13ag [00314] [00315] [00316] 39 [2113-57-7] 13ah [00317] [00318] [00319] 64 [2113-57-7] 13ai [00320] [00321] [00322] 28 [591-50-4] 13aj [00323] [00324] [00325] 31 [103068-20-8] 13ak [00326] [00327] [00328] 47 [864377-31-1] 13al [00329] [00330] [00331] 51 [591-51-4] 2.0 eq

Example 5

Synthesis of (6-Bromo-1,1,2,2,3,3-hexamethyl-indan-5-yl)-(1,1,2,2,3,3-hexamethyl-indan-5-yl)-amine (17a)

[0108] ##STR00332##

Synthesis of (1,1,2,2,3,3-Hexamethyl-indan-5-yl)-carbamic acid tert-butyl ester (14a)

[0109] 50.0 g (178 mmol, 1.0 eq) 5-Bromo-1,1,2,2,3,3-hexamethyl-indan5-Bromo-1,1,2,2,3,3-hexamethyl-indan 1a, 31.2 g (267 mmol, 1.5 eq) tert.-butylcarbamate and 146 g (356 mmol, 2.0 eq) cesium carbonate are dissolved in 750 ml tert.-butanol and degassed for 20 minutes. Then, 6.52 g (7.12 mmol, 0.04 eq) Tris(dibenzylideneacetone)dipalladium(0) and 4.38 g (10.7 mmol, 0.04 eq) S-Phos are added and the mixture refluxed overnight. After the reaction is finished, the solvent is removed in vacuo. 52.0 g (164 mmol, 92%) brownish oil are obtained.

Synthesis of 1,1,2,2,3,3-Hexamethyl-indan-5-ylamine (15a)

[0110] 52.0 g (164 mmol, 1.0 eq) (1,1,2,2,3,3-Hexamethyl-indan-5-yl)-carbamic acid tert-butyl ester 14a are dissolved in 500 ml dichloromethan and treated with 63.2 ml (820 mmol, 5.0 eq) trifluoroacetic acid. The reaction is stirred at room temperature for 14 hours and after the reaction is finished, the solvent is evaporated, the crude is re-dissolved in ethylacetate and washed with sodium carbonate. The solution is dried over sodium sulfate and the solvent removed in vacuo. 31.7 g (146 mmol, 89%) of desired product 15a are obtained as slightly brownish oil.

Synthesis of (6-Bromo-1,1,2,2,3,3-hexamethyl-indan-5-yl)-(1,1,2,2,3,3-hexamethyl-indan-5-yl)-amine (17a)

[0111] In a 2 L four-necked flask 30.0 g (138 mmol, 1.0 eq) of 1,1,2,2,3,3-Hexamethyl-indan-5-ylamine 15a are dissolved together with 53.3 g (148 mmol, 1.07 eq) 5,6-dibromo-2,3-dihydro-1,1,2,2,3,3-hexamethyl-1H-Indene [1541101-19-2] 16a and 35.5 g (359 mmol, 2.6 eq) sodium-tert-butoxide in 600 ml of dried toluene. The mixture is degassed for 30 minutes and then, 310 mg (1.38 mmol, 0.01 eq) of palladium(II)-acetate and 765 mg (1.38 mmol, 0.01 eq) 1,1-bis(diphenylphosphino)ferrocene are added. The reaction is heated to 100 C. for 12 hours. After the reaction is finished, 200 ml water are added and the mixture stirred for additional 45 min. Then, the aqueous phase is separated and the organic phase is washed 3 times with water. The combined aqueous layers are extracted once with toluene. The combined organic layers are dried over sodium sulfate and the solvent is removed in vacuo. 43.2 g (86.9 mmol, 63%) of desired secondary amine 17a are obtained as brownish oil.

[0112] Analogously the following compounds can be obtained:

TABLE-US-00004 Yield Comp. Educt Educt Product [%] 17b [00333] [00334] [00335] 45 [108714-73-4] [1541101-19-2] 17c [00336] [00337] [00338] 65 [4106-66-5] [1541101-19-2] 17d [00339] [00340] [00341] 78 [50548-43-1] [1541101-19-2] 17e [00342] [00343] [00344] 62 [1579281-06-3] [1541101-19-2] 17f [00345] [00346] [00347] 71 [133872-22-7] [1541101-19-2] 17g [00348] [00349] [00350] 52 [1257982-95-8] [1541101-19-2] 17h [00351] [00352] [00353] 59 [855180-11-9] [1541101-19-2] 17i [00354] [00355] [00356] 83 [71041-19-5] [1541101-19-2]

Example 6

Synthesis of Compound 18a

[0113] A 1 L four-necked flask is charged with 43.0 g (86.6 mmol, 1.0 eq) of 17a, 29.9 g (217 mmol, 2.5 eq) potassium carbonate and 500 ml of 1-methyl-2-pyrrolidon. After the mixture is degassed for 25 minutes, 2.65 g (26.0 mmol, 0.30 eq) pivalic acid, 389 mg (1.73 mmol, 0.02 eq) palladium(II)-acetate and 3.46 ml (3.46 mmol, 0.04 eq) of a 1 mol/l tri-tert.-butylphoshine solution in toluene are added. The reaction is stirred overnight at 130 C. and after the reaction is finished, the solvent and the pivalic acid are removed in vacuo and the remaining solid is dissolved in 50 ml toluene. The solution is washed 3 times with 75 ml water and dried over sodium sulfate. After evaporation of the solvent the crude product is purified by crystallization from n-heptane/toluene. 23.7 g (56.9 mmol, 66%) of product 18a are obtained as light-brown crystals.

[0114] Analogously the following compounds can be obtained:

TABLE-US-00005 Yield Comp. Educt Product [%] 18b [00357] [00358] 37 18c [00359] [00360] 24 18d [00361] [00362] 74 18e [00363] [00364] 88 18f [00365] [00366] 38 18g [00367] [00368] 21 18h [00369] [00370] 91 18i [00371] [00372] 42

Example 7

Synthesis of compound 20a

[0115] 25.0 g (56.9 mmol, 1.00 eq) 7-Bromo-12,12-dimethyl-10-phenyl-10,12-dihydro-10-aza-indeno[2,1-b]fluorine 19a are dissolved with 23.7 g 56.9 mmol, 1.00 eq) of educt 18a and 8.46 g (85.3 mmol, 1.50 eq) sodium-t-butoxide in 500 ml of dried toluene. After the reaction is degassed for 30 minutes 1.30 g (1.42 mmol, 0.03 eq) Tris(dibenzylideneacetone)di-palladium(0) and 2.84 ml (2.84 mmol, 0.05 eq) tri-tert-butylphosphine solution are added. The mixture is refluxed overnight and after the reaction is finished the solution is concentrated in vacuo. The precipitate is filtered and washed with water and ethanol. The product is purified by hot extraction with heptane/toluene 3:1 and three times recrystallized with toluene/heptane. After two sublimations 19.8 g (25.6 mmol, 45%) of final product 20a are obtained as a colorless solid in a purity >99.9% (HPLC).

[0116] Analogously the following compounds can be obtained:

TABLE-US-00006 Yield Comp. Educt Educt Product [%] 20b [00373] [00374] [00375] 56 [103068-20-8] 20c [00376] [00377] [00378] 61 [1153-85-1] 20d [00379] [00380] [00381] 34 [955959-84-9] 20e [00382] [00383] [00384] 45 [86437-31-1] 20f [00385] [00386] [00387] 17 [591-50-4 20g [00388] [00389] [00390] 37 [1153-85-1] 20h [00391] [00392] [00393] 47 [591-50-4 20i [00394] [00395] [00396] 21 [864377-31-1] 20j [00397] [00398] [00399] 29 [864377-31-1] 20k [00400] [00401] [00402] 53 [591-50-4 20l [00403] [00404] [00405] 26 [23449-08-3] 20m [00406] [00407] [00408] 44 [2113-57-7]

Example 8

Synthesis of Compound 22a

[0117] To a suspension of 1.73 g (43.3 mmol, 1.2 eq) 60 wt-% sodium hydride in 50 ml dried DMF 15.0 g (36.1 mmol, 1.0 eq) of educt 20a in 50 ml dried DMF are added slowly. After the reaction is finished 9.66 g (36.1 mmol, 1.0 eq) of 2-Chloro-4,6-diphenyl-[1,3,5]triazine in another 50 ml of toluene are added to the mixture. After stirring overnight 100 ml water are added drop-wise and the precipitate filtered, washed with water and ethanol and dried in vacuo. The product is purified by hot extraction with heptane/toluene 1:1 and two times recrystallized with toluene/heptane. After two sublimations 7.30 g (11.3 mmol, 31%) of final product 20a are obtained as a colorless solid in a purity >99.9% (HPLC).

[0118] Analogously the following compounds can be obtained:

TABLE-US-00007 Yield Comp. Educt Educt Product [%] 22b [00409] [00410] [00411] 45 [3842-55-5] 22c [00412] [00413] [00414] 61 [2915-16-4] 22d [00415] [00416] [00417] 22 [3842-55-5] 22e [00418] [00419] [00420] 38 [2915-16-4] 22f [00421] [00422] [00423] 12 [3842-55-5] 22g [00424] [00425] [00426] 19 [3842-55-5]

Example 9

Device Preparation and Characterization

[0119] The following examples V1 to E13 (see Table 1 and 2) show data of various OLEDs.

Substrate Pre-Treatment of Examples V1-E13:

[0120] Glass plates with structured ITO (50 nm, indium tin oxide) are coated with 20 nm PEDOT:PSS (Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate, CLEVIOS P VP Al 4083 from Heraeus Precious Metals GmbH Germany, spin-coated from a water-based solution) and form the substrates on which the OLEDs are processed.

[0121] The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The exact layer structure is denoted in Table 1. The materials used for the OLED fabrication are presented in Table 3.

[0122] 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 IC1:M1:TEG1 (55%:35%:10%) here means that material IC1 is present in the layer in a proportion by volume of 55%, M1 is present in the layer in a proportion of 35% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

[0123] The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (CE1000, measured in cd/A at 1000 cd/m.sup.2), the luminous efficacy (LE1000, measured in lm/W at 1000 cd/m.sup.2), the external quantum efficiency (EQE1000, measured in % at 1000 cd/m.sup.2) and the voltage (U1000, measured at 1000 cd/m.sup.2 in V) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines) assuming a Lambertian emission profile. The electroluminescence (EL) spectra are recorded at a luminous density of 1000 cd/m.sup.2 and the CIE 1931 x and y coordinates are then calculated from the EL spectrum.

[0124] The device data of various OLEDs is summarized in Table 2. The example V1 is a comparison example according to the state-of-the-art. The examples E1-E13 show data of inventive OLEDs.

[0125] In the following section several examples are described in more detail to show the advantages of the inventive OLEDs.

Use of Inventive Compounds as Host Material in Phosphorescent OLEDs

[0126] The use of the inventive compounds as host material results in significantly improved OLED device data compared to state-of-the-art materials, especially with respect to device efficiency.

[0127] The use of the inventive material 13a as host mixed with IC1 results in 10% improved external quantum efficiency compared to a device containing the material IC3 (comparison of example V1 with E1).

TABLE-US-00008 TABLE 1 OLED layer structure HIL IL HTL EBL EML HBL ETL Bsp. Dicke Dicke Dicke Dicke Dicke Dicke Dicke V1 - - - SpA1 HATCN SpMA1 IC1:IC3:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (65%:30%:5%) 30 nm 10 nm 30 nm E1 - - - SpA1 HATCN SpMA1 IC1:13a:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (65%:30%:5%) 30 nm 10 nm 30 nm E2 - - - SpA1 HATCN SpMA1 IC1:13f:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm E3 - - - SpA1 HATCN SpMA1 13v:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E4 SpA1 HATCN SpMA1 13aa IC1:IC3:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 80 nm 10 nm (25%:65%:10%) 30 nm 10 nm 30 nm E5 - - - SpA1 HATCN SpMA1 IC1:13ag:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (35%:55%:10%) 30 nm 10 nm 30 nm E6 - - - SpA1 HATCN SpMA1 IC1:13aj:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (35%:55%:10%) 30 nm 10 nm 30 nm E7 - - - SpA1 HATCN SpMA1 IC1:20g:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:50%:5%) 30 nm 10 nm 30 nm E8 - - - SpA1 HATCN SpMA1 IC1:20h:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:50%:5%) 30 nm 10 nm 30 nm E9 - - - SpA1 HATCN SpMA1 20j:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E10 SpA1 HATCN SpMA1 20 m IC1:IC3:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 80 nm 10 nm (25%:65%:10%) 30 nm 10 nm 30 nm E11 - - - SpA1 HATCN SpMA1 22c:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E12 - - - SpA1 HATCN SpMA1 22f:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm E13 - - - SpA1 HATCN SpMA1 IC1:13p:TEG1 IC1 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm

TABLE-US-00009 TABLE 2 OLED device data U1000 CE1000 LE1000 EQE CIE x/y at Example (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 V1 3.3 60 57 16.1% 0.32/0.64 E1 3.4 66 61 17.8% 0.32/0.63 E2 3.5 63 57 16.9% 0.32/0.64 E3 3.8 60 50 16.5% 0.32/0.63 E4 3.6 55 48 15.2% 0.31/0.64 E5 3.7 60 51 16.7% 0.33/0.63 E6 3.8 62 51 16.9% 0.34/0.63 E7 3.6 63 55 17.1% 0.33/0.63 E8 3.7 64 54 17.3% 0.33/0.63 E9 3.3 55 52 15.5% 0.32/0.63 E10 3.4 59 55 15.9% 0.33/0.63 E11 3.6 60 52 16.4% 0.32/0.63 E12 3.6 58 51 15.7% 0.33/0.63 E13 3.5 61 55 16.7% 0.32/0.64

TABLE-US-00010 TABLE 3 Chemical structures of the OLED materials [00427] HATCN [00428] SpA1 [00429] SpMA1 [00430] LiQ [00431] IC1 [00432] TEG1 [00433] ST2 [00434] IC3 [00435] 13a [00436] 13f [00437] 13v [00438] 13aa [00439] 13ag [00440] 13aj [00441] 20g [00442] 20h [00443] 20j [00444] 20m [00445] 22c [00446] 22f [00447] 13p