Phosphorescent OLED and hole transporting materials for phosphorescent OLEDS

Abstract

The present invention relates to phosphorescent organic light-emitting diodes (OLEDs) including a hole-transporting or a hole-transporting and an electron-blocking layer including an N,N,N,N-tetraaryl-phenylene-3,5-diamine or an N,N,N,N-tetraaryl-1,1-biphenyl-3,3-diamine matrix compound and to new N,N,N,N-tetraarylsubstituted m-arylene diamine compounds useful as hole-transporting and electron-blocking layer matrices in phosphorescent OLEDs.

Claims

1. A compound represented by general formula (I) ##STR00046## wherein R.sup.1-R.sup.20 are independently selected from hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl; i) at least one of R.sup.1-R.sup.5 and at least one of R.sup.11-R.sup.15 is C6-C20 aryl or C2-C20 heteroaryl, ii) R.sup.1 with R.sup.2 as well as R.sup.11 with R.sup.12 form an aromatic ring, or iii) R.sup.2 with R.sup.3 as well as R.sup.12 with R.sup.13 form an aromatic ring; at least two of R.sup.6-R.sup.10 and at least two of R.sup.16-R.sup.20 are methyl, or at least one of R.sup.6-R.sup.10 and at least one of R.sup.16-R.sup.20 is selected from C2-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl, and x is an integer selected from 0 or 1, wherein when x is 0, R.sup.22 is selected from C3-C20 cycloalkyl, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C2-C20 heteroaryl, wherein when x is 1, R.sup.21 and R.sup.22 are independently selected from C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, or C3-C10 cycloalkyloxy.

2. The compound according to claim 1, wherein i) at least one of R.sup.1-R.sup.5 and at least one of R.sup.11-R.sup.15 is C6-C20 aryl or C2-C20 heteroaryl, ii) R.sup.1 with R.sup.2 as well as R.sup.11 with R.sup.12 form an aromatic ring, or iii) R.sup.2 with R.sup.3 as well as R.sup.12 with R.sup.13 form an aromatic ring; at least two of R.sup.6-R.sup.10 and at least two of R.sup.6-R.sup.20 are methyl, or at least one of R.sup.6-R.sup.10 and at least one of R.sup.16-R.sup.20 is selected from C2-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl, whereas other R.sup.6-R.sup.10 and R.sup.16-R.sup.20 are H.

3. The compound according to claim 2, wherein at least one of R.sup.1-R.sup.5 and at least one of R.sup.11-R.sup.15 is C6-C20 aryl or C2-C20 heteroaryl; at least two of R.sup.6-R.sup.10 and at least two of R.sup.16-R.sup.20 are methyl, or at least one of R.sup.6-R.sup.10 and at least one of R.sup.16-R.sup.20 is selected from C2-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl, wherein other R.sup.1-R.sup.5, R.sup.6-R.sup.10, R.sup.11-R.sup.15 and R.sup.16-R.sup.20 are H.

4. The compound according to claim 3, wherein at least one of R.sup.1-R.sup.5 and at least one of R.sup.11-R.sup.15 is phenyl; at least two of R.sup.6-R.sup.10 and at least two of R.sup.16-R.sup.20 are methyl, or at least one of R.sup.6-R.sup.10 and at least one of R.sup.16-R.sup.20 is selected from C2-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl, wherein other R.sup.1-R.sup.5, R.sup.6-R.sup.10, R.sup.11-R.sup.15 and R.sup.16-R.sup.20 are H.

5. The compound according to claim 1, wherein the compound is represented by formula (III) ##STR00047## wherein Ar.sup.1 is selected from 4-tert-butylphenyl, 3,5-dimethylphenyl, or 2,4,6-trimethylphenyl, and R.sup.24 is selected from C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy or C3-C10 cycloalkyloxy.

6. A compound represented by general formula (I) ##STR00048## wherein R.sup.1-R.sup.20 are independently selected from hydrogen, C3-C20 cycloalkyl, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl; i) at least one of R.sup.1-R.sup.5 and at least one of R.sup.11-R.sup.15 is C6-C20 aryl or C2-C20 heteroaryl, ii) R.sup.1 with R.sup.2 as well as R.sup.11 with R.sup.12 form an aromatic ring, or iii) R.sup.2 with R.sup.3 as well as R.sup.12 with R.sup.13 form an aromatic ring; at least one of R.sup.6-R.sup.10 and at least one of R.sup.16-R.sup.20 is selected from C3-C20 cycloalkyl, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl, and x is an integer selected from 0 or 1, wherein when x is 0, R.sup.22 is selected from C3-C20 cycloalkyl, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl, wherein when x is 1, R.sup.21 and R.sup.22 are independently selected from C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, or C3-C10 cycloalkyloxy.

7. A compound represented by general formula (I) ##STR00049## wherein R.sup.1-R.sup.20 are independently selected from hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl; i) at least one of R.sup.1-R.sup.5 and at least one of R.sup.11-R.sup.15 is C6-C20 aryl or C2-C20 heteroaryl, ii) R.sup.1 with R.sup.2 as well as with R.sup.12 form an aromatic ring, or iii) R.sup.2 with R.sup.3 as well as R.sup.12 with R.sup.13 form an aromatic ring; at least two of R.sup.6-R.sup.10 and at least two of R.sup.16-R.sup.20 are methyl, or at least one of R.sup.6-R.sup.10 and at least one of R.sup.16-R.sup.20 is selected from C2-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl, and x is 1, wherein R.sup.21 and R.sup.22 are independently selected from C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, or C3-C10 cycloalkyloxy.

8. A compound represented by formula (II) ##STR00050## wherein R.sup.23 is hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C1-C10 alkoxy, C3-C20 cycloalkyloxy, C7-C20 arylalkyl, C6-C20 aryl, or C2-C20 heteroaryl, and Ar is selected from 4-tert-butylphenyl, 3,5-dimethylphenyl, or 2,4,6-trimethylphenyl.

9. The compound according to claim 8, represented by formula (IV): ##STR00051##

10. The compound according to claim 8, represented by formula (V): ##STR00052##

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1: Schematic drawing of experimental bottom emitting phosphorescent OLED

(2) FIG. 2: a) Top view of deposition of layer 1 (p-doped inventive material (stripes), p-doped reference (dots), left; b) Top view of layer 2 after rotation of substrate by 90, with the inventive material in the top row (fields A, C) and reference material in the bottom row (fields B, D).

(3) FIG. 3a3g: .sup.1H-NMR spectra of example compounds having formula (II) measured in CD.sub.2Cl.sub.2 solution, at 500.13 MHz, referenced to 5.31 ppm; 3aMDAB-1, 3bMDAB-2, 3cMDAB-3, 3dMDAB-4, 3eMDAB-5, 3f-MDAB-6, 3gMDAB-7.

(4) FIG. 4a4o: .sup.1H-NMR spectra of example compounds having formula (III) measured under the same conditions; 4aMPD-1, 4bMPD-2, 4cMPD-3, 4dMPD-4, 4eMPD-5, 4fMPD-6, 4gMPD-7, 4hMPD-8, 4iMPD-9, 4jMPD-10, 4kMPD-11, 4lMPD-12, 4m-MPD-13, 4nMPD-14, 4oMPD-15.

EXAMPLES

General Procedure for 3,5-dibromophenylenes

(5) 1,3,5-Tribromobenzene, the boronic acid and Pd(PPh.sub.3).sub.4 were dissolved in a mixture of toluene and ethanol. A degassed 2M aqueous Na.sub.2CO.sub.3 solution was added. The mixture was refluxed for 18 hours. After cooling to room temperature the organic phase was separated from the aqueous one. The aqueous phase was extracted with toluene three times. The combined organic phases were evaporated to dryness and the residue was filtered over a pad of silica gel using dichloromethane (DCM) as eluent. After evaporating the solvents the crude product was purified by column chromatography on silica gel using hexane:DCM mixtures as an eluent. In thin layer chromatography (TLC), the upper main spot was identified as the desired product and the one below as the 3,5-disubstituted bromobenzene side product.

3,5-dibromo-1,1-biphenyl

(6) ##STR00010##

(7) 1,3,5-tribromobenzene: 10.20 g (1.2 eq, 32.4 mmol)

(8) phenylboronic acid: 3.30 g (1.0 eq, 27.1 mmol)

(9) Pd(PPh.sub.3).sub.4: 625 mg (2 mol %, 0.54 mmol)

(10) toluene: 160 mL

(11) ethanol: 54 mL

(12) 2M Na.sub.2CO.sub.3: 27 mL

(13) Yield: 5.53 g (65%)

(14) GC-MS: m/z=310/312/314

3,5-dibromo-3,5-dimethyl-1,1-biphenyl

(15) ##STR00011##

(16) 1,3,5-tribromobenzene: 13.00 g (1.2 eq, 41.3 mmol)

(17) 3,5-dimethylphenylboronic acid: 5.16 g (1.0 eq, 34.4 mmol)

(18) Pd(PPh.sub.3).sub.4: 795 mg (2 mol %, 0.69 mmol)

(19) toluene: 160 mL

(20) ethanol: 68 mL

(21) 2M Na.sub.2CO.sub.3: 34 mL

(22) Yield: 7.13 g (61%)

(23) GC-MS: m/z=338/340/342

3,5-dibromo-1,1:4,1-terphenyl

(24) ##STR00012##

(25) 1,3,5-tribromobenzene: 10.00 g (1.2 eq, 31.77 mmol)

(26) 4-biphenylboronic acid: 5.24 g (1.0 eq, 26.47 mmol)

(27) Pd(PPh.sub.3).sub.4: 612 mg (2 mol %, 0.53 mmol)

(28) toluene: 160 mL

(29) ethanol: 52 mL

(30) 2M Na.sub.2CO.sub.3: 26 mL

(31) Yield: 4.95 g (48%)

(32) GC-MS: m/z=386/388/390

3,5-dibromo-3-(trifluoromethyl)-1,1-biphenyl

(33) ##STR00013##

(34) 1,3,5-tribromobenzene: 10.00 g (1.2 eq, 31.77 mmol)

(35) 3-(Trifluoromethyl)phenylboronic acid: 5.03 g (1.0 eq, 26.47 mmol)

(36) Pd(PPh.sub.3).sub.4: 611 mg (2 mol %, 0.53 mmol)

(37) toluene: 160 mL

(38) ethanol: 52 mL

(39) 2M Na.sub.2CO.sub.3: 26 mL

(40) Yield: 5.57 g (56%)

(41) GC-MS: m/z=378/380/382

3-(3,5-dibromophenyl)pyridine

(42) ##STR00014##

(43) 1,3,5-tribromobenzene: 10.00 g (1.2 eq, 31.77 mmol)

(44) 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine: 5.43 g (1.0 eq, 26.47 mmol)

(45) Pd(PPh.sub.3).sub.4: 612 mg (2 mol %, 0.53 mmol)

(46) toluene: 160 mL

(47) ethanol: 52 mL

(48) 2M Na.sub.2CO.sub.3: 26 mL

(49) Yield: 4.00 g (48%)

(50) GC-MS: m/z=311/313/315

General Procedure for Biphenyl Based Cores

(51) The dibromo compound was solved in ether and the flask was shielded from light by aluminium foil. The solution was cooled to 80 C. and butyllithium was added within 30 minutes. After butyllithium addition, the solution was kept at 80 C. for 90 minutes. Under vigorous stirring, copper(II) chloride was added in one shot. The solution was allowed to warm to room temperature and to stir overnight. TLC indicated consumption of the starting material and formation of a new product as the only component in the mixture. The mixture was washed three times with 10% aqueous NH.sub.4OH, once with brine and once with water. The organic phase was dried over MgSO.sub.4 and filtered through a pad of silica gel by using DCM/hexane 1:1. After evaporation of the solvents, the crude product was washed in boiling methanol for 15 minutes and then filtered and dried.

3,3-dibromo-1,1-biphenyl

(52) ##STR00015##

(53) 3,5-dibromobenzene: 58.98 g (1.0 eq, 250 mmol)

(54) n-Butyllithium, 2.5M in hexane: 100 mL (1.0 eq, 250 mmol)

(55) copper(II)chloride: 36.97 g (1.1 eq, 275 mmol)

(56) diethylether: 800 mL

(57) Yield: 22.06 g (56%)

(58) GC-MS: m/z=310/312/314

3,3-dibromo-5,5-dimethyl-1,1-biphenyl

(59) ##STR00016##

(60) 3,5-dibromotoluene: 62.48 g (1.0 eq, 250 mmol)

(61) n-Butyllithium, 2.5M in hexane: 100 mL (1.0 eq, 250 mmol)

(62) copper(II)chloride: 36.97 g (1.1 eq, 275 mmol)

(63) diethylether: 800 mL

(64) Yield: 22.1 g (52%)

(65) GC-MS: m/z=338/340/342

3,3-dibromo-5,5-dimethoxy-1,1-biphenyl

(66) ##STR00017##

(67) 3,5-dibromoanisole: 16.40 g (1.0 eq, 61.7 mmol)

(68) n-Butyllithium, 2.5M in hexane: 27 mL (1.0 eq, 67.8 mmol)

(69) copper(II)chloride: 9.12 g (1.1 eq, 67.8 mmol)

(70) diethylether: 200 mL

(71) Yield: 9.7 g (85%)

(72) GC-MS: m/z=370/372/374

General Procedure for Secondary Amines

(73) Under an inert atmosphere the bromoaryl component, palladium(II)acetate, cesium carbonate and 2,2-bis(diphenylphosphino)-1,1-binaphthyl (BINAP) were combined in a flask and dissolved in 1,4-dioxane. The primary arylamine component was added, followed by heating up the mixture to reflux and stirring for 18-48 hours. According to TLC the reaction was complete. The mixture was cooled to room temperature and filtered through a pad of silica gel. After washing with DCM and evaporation of the solvent the crude product was purified by column chromatography (SiO.sub.2, hexane:DCM mixtures). The combined fractions were evaporated to dryness and the resulting solid was recrystalized from hexane to yield the desired product.

N-(p-tolyl)naphthalen-2-amine

(74) ##STR00018##

(75) 2-bromonaphthalene: 15 g (1.0 eq, 72.44 mmol)

(76) p-toluidine: 11.6 g (1.5 eq, 108.6 mmol)

(77) palladium(II)acetate: 488 mg (3.0 mol. %, 2.17 mmol)

(78) BINAP: 2.0 g (4.5 mol. %, 3.26 mmol)

(79) cesium carbonate: 47.20 g (2.0 eq, 144.9 mmol)

(80) dioxane: 150 mL

(81) Yield: 11.4 g (67%)

(82) GC-MS: m/z=233

N-(4-(methyl)phenyl)-[1,1-biphenyl]-4-amine

(83) ##STR00019##

(84) 4-bromobiphenyl: 20.0 g (1.0 eq, 85.8 mmol)

(85) 4-toluidine: 9.65 g (1.05 eq, 90.1 mmol)

(86) palladium(II)acetate: 578 mg (3.0 mol. %, 2.6 mmol)

(87) BINAP: 2.40 g (4.5 mol. %, 3.9 mmol)

(88) cesium carbonate: 39.14 g (1.4 eq, 120.1 mmol)

(89) dioxane: 200 mL

(90) Yield: 19.20 g (86%)

(91) EI-MS: m/z=259

N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine

(92) ##STR00020##

(93) 4-bromobiphenyl: 20 g (1.0 eq, 85.8 mmol)

(94) 4-(tert-butyl)aniline: 15.36 g (1.2 eq, 102.9 mmol)

(95) palladium(II)acetate: 578 mg (3.0 mol. %, 2.57 mmol)

(96) BINAP: 2.4 g (4.5 mol. %, 3.86 mmol)

(97) cesium carbonate: 55.90 g (2.0 eq, 171.6 mmol)

(98) dioxane: 220 mL

(99) Yield: 13.9 g (54%)

(100) GC-MS: m/z=301

N-(3,5-dimethylphenyl)-[1,1-biphenyl]-4-amine

(101) ##STR00021##

(102) 4-bromobiphenyl: 30.00 g (1.0 eq, 128.70 mmol)

(103) 3,5-dimethylaniline: 16.38 g (1.05 eq, 135.10 mmol)

(104) palladium(II)acetate: 867 mg (3.0 mol. %, 3.86 mmol)

(105) BINAP: 3.60 g (4.5 mol. %, 5.79 mmol)

(106) cesium carbonate: 58.70 g (1.4 eq, 180.00 mmol)

(107) dioxane: 300 mL

(108) Yield: 21.34 g (60%)

(109) GC-MS: m/z=273

N-mesityl-[1,1-biphenyl]-4-amine

(110) ##STR00022##

(111) 4-bromobiphenyl: 20.00 g (1.0 eq, 85.8 mmol)

(112) mesitylamine: 12.18 g (1.05 eq, 90.1 mmol)

(113) palladium(II)acetate: 578 mg (3.0 mol. %, 2.57 mmol)

(114) BINAP: 2.40 g (4.5 mol. %, 3.86 mmol)

(115) cesium carbonate: 39.13 g (1.4 eq, 120.1 mmol)

(116) dioxane: 200 mL

(117) Yield: 12.53 g (51%)

(118) GC-MS: m/z=287

General Procedure for Tertiary Amines of the 3,5-diaminophenylene Class

(119) Under an inert atmosphere, the secondary amine, the dibromo compound, bis(dibenzylidenaceton)palladium, tri-tert-butylphosphine and potassium-tert-butoxide were combined in a flask and solved in toluene. The mixture was stirred at 80 C. for 80 minutes and then cooled to room temperature. TLC indicated complete consumption of the starting materials. The mixture was filtered through a pad of silica gel, washed with a 1:2 mixture of DCM/hexane and evaporated to dryness. The crude product was stirred in boiling methanol. After cooling to room temperature, the mixture was filtered to yield the product. In case TLC indicated still some impurities, column chromatography was used. Finally, all tertiary amines were purified by gradient sublimation under high vacuum (10.sup.6 mbar) condition.

N1,N3-di([1,1-biphenyl]-4-yl)-N1,N3-bis(4-(tert-butyl)phenyl)-5-methylbenzene-1,3-diamine (MPD-1)

(120) ##STR00023##

(121) 3,5-dibromotoluene: 2.8 g (1.0 eq, 11.2 mmol)

(122) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 7.1 g (2.1 eq, 23.6 mmol)

(123) bis(dibenzylidenaceton)palladium: 129 mg (2 mol. %, 0.22 mmol)

(124) tri-tert-butylphosphine: 68 mg (3 mol. %, 0.34 mmol)

(125) potassium-tert-butoxide: 3.77 g (3.0 eq, 33.6 mmol)

(126) toluene: 220 mL

(127) Yield: 7.03 g (91%)

(128) HPLC-MS: m/z=691 [M+H.sup.+]

5-methyl-N1,N3-di(naphthalen-2-yl)-N1,N3-di-p-tolylbenzene-1,3-diamine (MPD-2) (Comparative Example)

(129) ##STR00024##

(130) 3,5-dibromotoluene: 2.0 g (1.0 eq, 8.0 mmol)

(131) N-(p-tolyl)naphthalen-2-amine: 3.92 g (2.1 eq, 16.8 mmol)

(132) bis(dibenzylidenaceton)palladium: 92 mg (2.0 mol. %, 0.16 mmol)

(133) tri-tert-butylphosphine: 49 mg (3 mol. %, 0.24 mmol)

(134) potassium-tert-butoxide: 2.69 g (3.0 eq, 24 mmol)

(135) toluene: 130 mL

(136) Yield: 3.95 g (70%)

(137) HPLC-MS: m/z=555 [M+H.sup.+]

5-methyl-N1,N3-di(naphthalen-1-yl)-N1,N3-diphenylbenzene-1,3-diamine (MPD-3) (Comparative Example)

(138) ##STR00025##

(139) 3,5-dibromotoluene: 5.0 g (1.0 eq, 20.0 mmol)

(140) N-phenylnaphthalen-1-amine: 9.21 g (2.1 eq, 42.0 mmol)

(141) bis(dibenzylidenaceton)palladium: 230 mg (2 mol %, 0.40 mmol)

(142) tri-tert-butylphosphine: 121 mg (3 mol. %, 0.60 mmol)

(143) potassium-tert-butoxide: 6.73 g (3.0 eq, 60.0 mmol)

(144) toluene: 150 mL

(145) Yield: 9.31 g (88%)

(146) HPLC-MS: m/z=527 [M+H.sup.+]

N1,N3-di([1,1-biphenyl]-4-yl)-N1,N3-bis(4-(tert-butyl)phenyl)-5-methoxybenzene-1,3-d (MPD-4)

(147) ##STR00026##

(148) 3,5-dibromoanisole: 2.00 g (1.0 eq, 7.50 mmol)

(149) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 4.76 g (2.1 eq, 15.8 mmol)

(150) bis(dibenzylidenaceton)palladium: 86 mg (2.0 mol %, 0.15 mmol)

(151) tri-tert-butylphosphine: 46 mg (3 mol. %, 0.23 mmol)

(152) potassium-tert-butoxide: 2.52 g (3.0 eq, 22.5 mmol)

(153) toluene: 130 mL

(154) Yield: 5.08 g (96%)

(155) HPLC-MS: m/z=707 [M+H.sup.+]

N3,N5-di([1,1-biphenyl]-4-yl)-N3,N5-bis(3,5-dimethylphenyl)-[1,1-biphenyl]-3,5-diamine (MPD-5)

(156) ##STR00027##

(157) 3,5-dibromo-1,1-biphenyl: 1.9 g (1.0 eq, 6.1 mmol)

(158) N-(3,5-dimethylphenyl)-[1,1-biphenyl]-4-amine: 3.5 g (2.1 eq, 12.8 mmol)

(159) bis(dibenzylidenaceton)palladium: 70 mg (2 mol. %, 0.12 mmol)

(160) tri-tert-butylphosphine: 37 mg (3 mol. %, 0.18 mmol)

(161) potassium-tert-butoxide: 2.05 g (3.0 eq, 18.3 mmol)

(162) toluene: 150 mL

(163) Yield: 2.94 g (69%)

(164) HPLC-MS: m/z=719 [M+Na.sup.+]

N3,N5-di([1,1-biphenyl]-4-yl)-N3,N5-bis(4-(tert-butyl)phenyl)-[1,1-biphenyl]-3,5-diamine (MPD-6)

(165) ##STR00028##

(166) 3,5-dibromo-1,1-biphenyl: 1.80 g (1.0 eq, 5.8 mmol)

(167) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 3.65 g (2.1 eq, 12.1 mmol)

(168) bis(dibenzylidenaceton)palladium: 66 mg (2 mol. %, 0.12 mmol)

(169) tri-tert-butylphosphine: 35 mg (3 mol. %, 0.17 mmol)

(170) potassium-tert-butoxide: 1.94 g (3.0 eq, 17.3 mmol)

(171) toluene: 150 mL

(172) Yield: 4.17 g (96%)

(173) HPLC-MS: m/z=775 [M+Na.sup.+]

N1,N3-di([1,1-biphenyl]-4-yl)-N1,N3-bis(3,5-dimethylphenyl)-5-methylbenzene-1,3-diamine (MPD-7)

(174) ##STR00029##

(175) 3,5-dibromotoluene: 1.52 g (1.0 eq, 6.1 mmol)

(176) N-(3,5-dimethylphenyl)-[1,1-biphenyl]-4-amine: 3.50 g (2.1 eq, 12.8 mmol)

(177) bis(dibenzylidenaceton)palladium: 70 mg (2 mol. %, 0.12 mmol)

(178) tri-tert-butylphosphine: 37 mg (3 mol. %, 0.18 mmol)

(179) potassium-tert-butoxide: 2.05 g (3.0 eq, 18.3 mmol)

(180) toluene: 150 mL

(181) Yield: 3.42 g (78%)

(182) HPLC-MS: m/z=657 [M+Na.sup.+]

N3,N5-di([1,1-biphenyl]-4-yl)-N3,N5-bis(3,5-dimethylphenyl)-3,5-dimethyl-[1,1-biphenyl]-3,5-diamine (MPD-8)

(183) ##STR00030##

(184) 3,5-dibromo-3,5-dimethyl-1,1-biphenyl: 2.00 g (1.0 eq, 5.88 mmol)

(185) N N-(3,5-dimethylphenyl)-[1,1-biphenyl]-4-amine: 3.38 g (2.1 eq, 12.4 mmol)

(186) bis(dibenzylidenaceton)palladium: 68 mg (2 mol. %, 0.12 mmol)

(187) tri-tert-butylphosphine: 36 mg (3 mol. %, 0.18 mmol)

(188) potassium-tert-butoxide: 1.98 g (3.0 eq, 17.6 mmol)

(189) toluene: 120 mL

(190) Yield: 4.02 g (94%)

(191) HPLC-MS: m/z=747 [M+Na.sup.+]

N3,N5-di([1,1-biphenyl]-4-yl)-N3,N5-bis(4-(tert-butyl)phenyl)-3,5-dimethyl-[1,1-biphenyl]-3,5-diamine (MPD-9)

(192) ##STR00031##

(193) 3,5-dibromo-3,5-dimethyl-1,1-biphenyl: 2.00 g (1.0 eq, 5.88 mmol)

(194) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 3.72 g (2.1 eq, 12.4 mmol)

(195) bis(dibenzylidenaceton)palladium: 68 mg (2 mol. %, 0.12 mmol)

(196) tri-tert-butylphosphine: 36 mg (3 mol. %, 0.18 mmol)

(197) potassium-tert-butoxide: 1.98 g (3.0 eq, 17.6 mmol)

(198) toluene: 120 mL

(199) Yield: 4.43 g (97%)

(200) HPLC-MS: m/z=803 [M+Na.sup.+]

N1,N3-di([1,1-biphenyl]-4-yl)-N1,N3-bis(4-(tert-butyl)phenyl)-5-(pyridin-3-yl)benzene-1,3-diamine (MPD-10)

(201) ##STR00032##

(202) 3-(3,5-dibromophenyl)pyridine: 1.50 g (1.0 eq, 4.8 mmol)

(203) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 3.0 g (2.1 eq, 10.1 mmol)

(204) bis(dibenzylidenaceton)palladium: 55 mg (2 mol. %, 0.10 mmol)

(205) tri-tert-butylphosphine: 29 mg (3 mol. %, 0.14 mmol)

(206) potassium-tert-butoxide: 1.62 g (3.0 eq, 14.4 mmol)

(207) toluene: 120 mL

(208) Yield: 2.40 g (66%)

(209) HPLC-MS: m/z=754 [M+H.sup.+]

N3,N5-di([1,1-biphenyl]-4-yl)-N3,N5-bis(4-(tert-butyl)phenyl)-3-(trifluoromethyl)-[1,1-biphenyl]-3,5-diamine (MPD-11)

(210) ##STR00033##

(211) 3,5-dibromo-3-(trifluoromethyl)-1,1-biphenyl: 1.82 g (1.0 eq, 4.8 mmol)

(212) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 3.0 g (2.1 eq, 10.1 mmol)

(213) bis(dibenzylidenaceton)palladium: 55 mg (2 mol. %, 0.10 mmol)

(214) tri-tert-butylphosphine: 29 mg (3 mol. %, 0.14 mmol)

(215) potassium-tert-butoxide: 1.62 g (3.0 eq, 14.4 mmol)

(216) toluene: 120 mL

(217) Yield: 3.29 g (84%)

(218) HPLC-MS: m/z=843 [M+Na.sup.+]

N3,N5-di([1,1-biphenyl]-4-yl)-N3,N5-bis(4-(tert-butyl)phenyl)-[1,1:4,1-terphenyl]-3,5-diamine (MPD-12)

(219) ##STR00034##

(220) 3,5-dibromo-1,1:4,1-terphenyl: 1.86 g (1.0 eq, 4.8 mmol)

(221) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 3.03 g (2.1 eq, 10.1 mmol)

(222) bis(dibenzylidenaceton)palladium: 55 mg (2 mol. %, 0.10 mmol)

(223) tri-tert-butylphosphine: 29 mg (3 mol. %, 0.14 mmol)

(224) potassium-tert-butoxide: 1.62 g (3.0 eq, 14.4 mmol)

(225) toluene: 120 mL

(226) Yield: 3.20 g (80%)

(227) HPLC-MS: m/z=851 [M+Na.sup.+]

N1,N3-di([1,1-biphenyl]-4-yl)-N1,N3-bis(4-(tert-butyl)phenyl)benzene-1,3-diamine (MPD-13)

(228) ##STR00035##

(229) 3,5-dibromobenzene: 2.5 g (1.0 eq, 10.6 mmol)

(230) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 6.70 g (2.1 eq, 22.26 mmol)

(231) bis(dibenzylidenaceton)palladium: 121 mg (2 mol. %, 0.21 mmol)

(232) tri-tert-butylphosphine: 64 mg (3 mol. %, 0.32 mmol)

(233) potassium-tert-butoxide: 3.57 g (3.0 eq, 31.8 mmol)

(234) toluene: 180 mL

(235) Yield: 6.70 g (94%)

(236) ESI-MS: m/z=677 [M+H.sup.+]

N1,N3-di([1,1-biphenyl]-4-yl)-N1,N3-bis(3,5-dimethylphenyl)benzene-1,3-diamine (MPD-14)

(237) ##STR00036##

(238) 3,5-dibromobenzene: 2.5 g (1.0 eq, 10.6 mmol)

(239) N-(3,5-dimethylphenyl)-[1,1-biphenyl]-4-amine: 6.08 g (2.1 eq, 22.26 mmol)

(240) bis(dibenzylidenaceton)palladium: 122 mg (2 mol. %, 0.21 mmol)

(241) tri-tert-butylphosphine: 64 mg (3 mol. %, 0.32 mmol)

(242) potassium-tert-butoxide: 3.57 g (3.0 eq, 31.8 mmol)

(243) toluene: 180 mL

(244) Yield: 5.42 g (82%)

(245) ESI-MS: m/z=621 [M+H.sup.+]

N1,N3-di([1,1-biphenyl]-4-yl)-5-methyl-N1,N3-di-p-tolylbenzene-1,3-diamine (MPD-15)

(246) ##STR00037##

(247) 3,5-dibromotoluene: 2.5 g (1.0 eq, 10.0 mmol)

(248) N-(4-(methyl)phenyl)-[1,1-biphenyl]-4-amine: 5.45 g (2.1 eq, 21.00 mmol)

(249) bis(dibenzylidenaceton)palladium: 115 mg (2 mol. %, 0.20 mmol)

(250) tri-tert-butylphosphine: 61 mg (3 mol. %, 0.30 mmol)

(251) potassium-tert-butoxide: 3.37 g (3.0 eq, 30.0 mmol)

(252) toluene: 180 mL

(253) Yield: 4.95 g (81%).

(254) ESI-MS: m/z=607 [M+H.sup.+]

N1,N3-di([1,1-biphenyl]-4-yl)-N1,N3-dimesityl-5-methylbenzene-1,3-diamine (MPD-16)

(255) ##STR00038##

(256) 3,5-dibromotoluene: 16.60 g (1.0 eq, 66.4 mmol)

(257) N-mesityl-[1,1-biphenyl]-4-amine: 40.1 g (2.1 eq, 139.5 mmol)

(258) bis(dibenzylidenaceton)palladium: 764 mg (2 mol. %, 1.3 mmol)

(259) tri-tert-butylphosphine: 404 mg (3 mol. %, 2.00 mmol)

(260) potassium-tert-butoxide: 22.36 g (3.0 eq, 199.3 mmol)

(261) toluene: 400 mL

(262) Yield: 22.3 g (51%)

(263) HPLC-MS: m/z=663 [M+H.sup.+]

General Procedure for Tertiary Amines of the 3,3-diaminobiphenylene Class

(264) The dibromo compound, the secondary amine, bis(dibenzylidenaceton)palladium, tri-tert-butylphosphine and potassium-tert-butoxide were combined in a flask and solved in toluene. The mixture was stirred at 80 C. until TLC indicated complete consumption of the starting materials. The mixture was filtered through a pad of silica gel, washed with DCM and evaporated to dryness. The crude solid was washed in boiling methanol and filtered afterwards. This sequence was repeated with hot hexane and hot acetone to yield the desired product finally.

N3,N3-di([1,1-biphenyl]-4-yl)-N3,N3-bis(4-(tert-butyl)phenyl)-5,5-dimethyl-[1,1-biphenyl]-3,3-diamine (MDAB-1)

(265) ##STR00039##

(266) 3,3-dibromo-5,5-dimethyl-1,1-biphenyl: 2.00 g (1.0 eq, 5.88 mmol)

(267) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 3.90 g (2.1 eq, 12.9 mmol)

(268) bis(dibenzylidenaceton)palladium: 68 mg (2.0 mol. %, 0.12 mmol)

(269) tri-tert-butylphosphine: 36 mg (3.0 mol. %, 0.18 mmol)

(270) potassium-tert-butoxide: 1.98 g (3.0 eq, 17.6 mmol)

(271) toluene: 150 mL

(272) Yield: 2.27 g (49%)

(273) HPLC-MS: m/z=781 [M+H.sup.+]

N3,N3-di([1,1-biphenyl]-4-yl)-N3,N3-bis(4-(tert-butyl)phenyl)-5,5-dimethoxy-[1,1-biphenyl]-3,3-diamine (MDAB-2)

(274) ##STR00040##

(275) 3,3-dibromo-5,5-dimethoxy-1,1-biphenyl: 2.00 g (1.0 eq, 5.88 mmol)

(276) N-(4-(tert-butyl)phenyl)-[1,1-biphenyl]-4-amine: 3.56 g (2.2 eq, 11.8 mmol)

(277) bis(dibenzylidenaceton)palladium: 62 mg (2.0 mol. %, 0.11 mmol)

(278) tri-tert-butylphosphine: 33 mg (3.0 mol. %, 0.16 mmol)

(279) potassium-tert-butoxide: 1.81 g (3.0 eq, 16.1 mmol)

(280) toluene: 130 mL

(281) Yield: 3.33 g (76%)

(282) HPLC-MS: m/z=835 [M+Na.sup.+]

N3,N3-di([1,1-biphenyl]-4-yl)-N3,N3-bis(3,5-dimethylphenyl)-5,5-dimethyl-[1,1-biphenyl]-3,3-diamine (MDAB-3)

(283) ##STR00041##

(284) 3,3-dibromo-5,5-dimethyl-1,1-biphenyl: 5.43 g (1.0 eq, 15.96 mmol)

(285) N-(3,5-dimethylphenyl)-[1,1-biphenyl]-4-amine: 9.61 g (2.1 eq, 33.51 mmol)

(286) bis(dibenzylidenaceton)palladium: 184 mg (2.0 mol. %, 0.32 mmol)

(287) tri-tert-butylphosphine: 202 mg (3.0 mol. %, 0.48 mmol)

(288) potassium-tert-butoxide: 5.37 g (3.0 eq, 47.88 mmol)

(289) toluene: 250 mL

(290) Yield: 10.56 g (91%)

(291) HPLC-MS: m/z=747 [M+Na.sup.+]

N3,N3-di([1,1-biphenyl]-4-yl)-N3,N3-diphenyl-[1,1-biphenyl]-3,3-diamine (MDAB-4)

(292) ##STR00042##

(293) 3,3-dibromo-1,1-biphenyl: 3.39 g (1.0 eq, 10.88 mmol)

(294) N-(3,5-dimethylphenyl)-[1,1-biphenyl]-4-amine: 5.60 g (2.1 eq, 22.84 mmol)

(295) bis(dibenzylidenaceton)palladium: 125 mg (2.0 mol. %, 0.22 mmol)

(296) tri-tert-butylphosphine: 66 mg (3.0 mol. %, 0.33 mmol)

(297) potassium-tert-butoxide: 3.66 g (3.0 eq, 32.6 mmol)

(298) toluene: 190 mL

(299) Yield: 6.8 g (97%)

(300) EI-MS: m/z=640

5,5-dimethyl-N3,N3,N3,N3-tetra-m-tolyl-[1,1-biphenyl]-3,3-diamine (MDAB-5)

(301) ##STR00043##

(302) 3,3-dibromo-5,5-dimethyl-1,1-biphenyl: 2.50 g (1.0 eq, 7.35 mmol)

(303) -3,3-dimethyldiphenylamine: 3.05 g (2.1 eq, 15.44 mmol)

(304) bis(dibenzylidenaceton)palladium: 85 mg (2.0 mol. %, 0.15 mmol)

(305) tri-tert-butylphosphine: 45 mg (3.0 mol. %, 0.22 mmol)

(306) potassium-tert-butoxide: 2.50 g (3.0 eq, 22.05 mmol)

(307) toluene: 180 mL

(308) Yield: 2.8 g (66%)

(309) EI-MS: m/z=572

N3,N3-di([1,1-biphenyl]-4-yl)-N3,N3-dimesityl-5,5-dimethyl-[1,1-biphenyl]-3,3-diamine

(310) ##STR00044##

(311) 3,5-dibromo-3,5-dimethyl-1,1-biphenyl: 20.00 g (1.0 eq, 58.8 mmol)

(312) N-mesityl-[1,1-biphenyl]-4-amine: 35.50 g (2.1 eq, 123.5 mmol)

(313) bis(dibenzylidenaceton)palladium: 676 mg (2 mol. %, 1.20 mmol)

(314) tri-tert-butylphosphine: 364 mg (3 mol. %, 1.80 mmol)

(315) potassium-tert-butoxide: 19.80 g (3.0 eq, 176.4 mmol)

(316) toluene: 700 mL

(317) Yield: 27.1 g (61%)

(318) HPLC-MS: m/z=753 [M+H.sup.+]

N3,N3-di([1,1-biphenyl]-4-yl)-N3,N3-dimesityl-[1,1-biphenyl]-3,3-diamine (MDAB-7)

(319) ##STR00045##

(320) 3,5-dibromo-1,1-biphenyl: 5.17 g (1.0 eq, 16.59 mmol)

(321) N-mesityl-[1,1-biphenyl]-4-amine: 10.00 g (2.1 eq, 34.79 mmol)

(322) bis(dibenzylidenaceton)palladium: 190 mg (2 mol. %, 0.33 mmol)

(323) tri-tert-butylphosphine: 100 mg (3 mol. %, 0.50 mmol)

(324) potassium-tert-butoxide: 5.58 g (3.0 eq, 49.77 mmol)

(325) toluene: 230 mL

(326) Yield: 8.7 g (72%)

(327) EI-MS: m/z=724

(328) OLED Preparation and Testing

(329) Performance testing of the new materials was carried out in bottom emitting phosphorescent organic light emitting diodes (OLED). The diodes were processed in vacuum via vapor thermal deposition of organic materials (active layers) and metals (electrodes). Shadow mask techniques were used to structure the devices (active matrix, electrodes). Four OLEDs are prepared on one substrate with an active area of 6.70 mm.sup.2 each. 16 identical indium tin oxide (ITO) substrates were processed at once in a 44 array placed on a table which is pivotable around its vertical axe. Using shutters, each of these 16 substrates can be covered by different set of organic layers. The ITO substrates were cleaned and put into a vapor thermal deposition unit in the 44 array. A reference p-doped layer (e.g. H-1 doped with D1; molar ratio (97:3) was deposited on half of these substrates for a final film thickness of 30 nm. On the other half of the plate, the studied inventive material was codeposited with the same p-dopant at the same 97:3 molar ratio and thickness. After a rotation of the plate by 90, the second (electron blocking) layer is deposited on top of the first layer. Here, half the plate is covered with 10 nm of the reference compound (e.g., TCTA) and the other half with the same inventive material as used in the first layer (see FIG. 1). The reference devices (FIG. 1, field D) were thus always processed together with the devices comprising the inventive materials. This approach allows assessing performance of new material in comparison with the reference independent from possible day-to-day variations of deposition rates, vacuum quality or other tool performance parameters. As each field contains 16 identically prepared OLEDs and the performance parameters were estimated for each of these 16 OLEDs, statistical evaluation of the obtained experimental results unequivocally showed the statistical significance of the observed average values reported in the Table 1.

(330) The subsequent phosphorescent green emission layer (Merck_TMM004:Irrpy at molar ratio 9:1) was deposited with a thickness of 20 nm, followed by 10 nm Merck_TMM004 as a hole blocking layer and 50 nm E-1 layer doped with D2 (matrix to dopant molar ratio 9:1). The cathode was prepared by vacuum deposition of 100 nm aluminum layer.

(331) Bottom emitting blue fluorescent OLEDs were prepared on ITO substrates and tested analogously, with a difference that Sun Fine Chem (SFC, Korea) host ABH113 and blue emitter NUBD370 were codeposited in the weight ratio 97:3 as a 20 nm thick emitting layer, followed by 36 nm thick electron transporting layer consisting of 60 weigt % E2 and 40 weight % lithium 8-hygroxyquinoline salt (LiQ). The 100 nm aluminium cathode was deposited on top of the electron transporting layer.

(332) In comparison with devices comprising H-2 in the same hole transporting and/or electron blocking layer, the devices comprising inventive compounds showed improvement in terms of the overall performance score Q as defined in the Table 1 in the range 3-22%.

(333) The features disclosed in the foregoing description and in the claims may, both separately and in any combination, be material for realizing the invention in diverse forms thereof.