Specifically substituted ladder type compounds for organic light emitting devices

Abstract

Specifically substituted ladder type compounds of formula (I) wherein A is formula (II) a material for an organic electroluminescence device comprising at least one compound of formula (I), and an organic electroluminescence device which comprises one or more organic thin film layers including an emitting layer between a cathode and an anode, wherein at least one layer of the organic thin film layers comprises at least one compound of formula (I). ##STR00001##

Claims

1. A compound of formula (I): ##STR00160## wherein A is ##STR00161## X.sub.A and X.sub.B each independently represent O or S; r represents 1, 2 or 3; in the case that r is 2 or 3, X.sub.B as well as Ar.sub.3 are the same or different in each occurrence; Ar.sub.1, Ar.sub.2 and Ar.sub.3 each independently represent a substituted or unsubstituted aromatic hydrocarbon group having a ring structure formed of 6 to 30 carbon atoms or a substituted or unsubstituted heterocyclic group having a ring structure formed of 5 to 30 atoms, and which is linked to one aromatic hydrocarbon group of Ar.sub.1, Ar.sub.2 and Ar.sub.3, respectively, via a carbon-carbon bond; L represents a single bond, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having a ring structure formed of 3 to 20 carbon atoms, a divalent silyl group having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group having a ring structure formed of 6 to 30 carbon atoms or a substituted or unsubstituted divalent heterocyclic group having a ring structure formed of 5 to 30 atoms; m is 1, 2 or 3; in the case that m is 2 or 3, L is the same or different in each occurrence; R.sup.17 is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having a ring formed of 3 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 24 carbon atoms; L.sub.1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having a ring structure formed of 3 to 20 carbon atoms, a divalent silyl group having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aromatic hydrocarbon group having a ring structure formed of 6 to 30 carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having a ring structure formed of 5 to 30 atoms; n is 1, 2 or 3; in the case that n is 2 or 3, L.sub.1 is the same or different in each occurrence; Ar.sub.4, Ar.sub.5, Ar.sub.6 and Ar.sub.7 each independently represent a substituted or unsubstituted aromatic hydrocarbon group having a ring structure formed of 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group having a ring structure formed of 5 to 30 atoms; wherein the dotted line is a bonding site.

2. The compound according to claim 1, wherein r is 1.

3. The compound according to claim 1, wherein m is 1.

4. The compound according to claim 1, wherein the compound of formula (I) has one of the following formulae: ##STR00162## ##STR00163## wherein X.sup.21 to X.sup.30 each independently represent CR.sub.X or N, R.sub.X is in each occurrence independently H, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having a ring formed of 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 24 carbon atoms, a silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having ring structure formed of 6 to 30 carbon atoms or a substituted or unsubstituted heterocyclic group having a ring structure formed of 5 to 30 atoms, or a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a cyano group or a halogen atom; wherein, among X.sup.21 to X.sup.30, if two or more atoms are CR.sub.X, any two of CR.sub.Xs are optionally bonded each other to form ring structures; wherein one of X.sup.21 to X.sup.30 in each formula (Ia), (Ib), (Ib′), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) and (Ij) represents a bonding site to (L).sub.m-A via a carbon atom.

5. The compound according to claim 4, wherein X.sup.21 to X.sup.30 each independently represent CR.sub.X.

6. The compound according to claim 1, wherein A is a group of the following formula: ##STR00164## X.sup.1 to X.sup.8 and Y.sup.1 to Y.sup.8 each independently represent CR.sub.Y or N, R.sub.Y is in each occurrence independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having a ring formed of 3 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 24 carbon atoms, a silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted hydrocarbon group having ring structure formed of 6 to 30 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having a ring structure formed of 5 to 30 atoms, or a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a cyano group or a halogen atom; wherein, among X.sup.1 to X.sup.8 and Y.sup.1 to Y.sup.8, if two or more atoms are CR.sub.Y, any two of CR.sub.Ys are optionally bonded each other to form ring structures wherein one of X.sup.5, X.sup.6, X.sup.7 or X.sup.8 and one of Y.sup.1, Y.sup.2, Y.sup.3 or Y.sup.4, are bonded to each other via L.sub.1.

7. The compound according to claim 1, wherein A is selected from the group consisting of the following formulae: ##STR00165##

8. The compound according to claim 7, wherein A is selected from the group consisting of the following formulae: ##STR00166##

9. The compound according to claim 1, wherein X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Y.sup.7 and Y.sup.8 is CR.sub.Y, wherein one of R.sub.Y at one of the positions X.sup.5 to X.sup.8 and one of R.sub.Y at the positions Y.sup.1 to Y.sup.4 are replaced by the group -(L.sub.1).sub.n-.

10. A material for an organic electroluminescence device, comprising the compound according to claim 1.

11. An organic electroluminescence device, comprising: one or more organic thin film layers comprising a light emitting layer between a cathode and an anode, wherein at least one of the one or more organic thin film layers comprises the compound according to claim 1.

12. The organic electroluminescence device according to claim 11, wherein the light emitting layer comprises a phosphorescent material, which is an ortho-metallated complex comprising a metal atom selected from the group consisting of iridium, osmium, and platinum.

13. The organic electroluminescence device according to claim 11, wherein a hole transporting layer is provided between the anode and the light emitting layer, and the hole transporting layer comprises the compound.

14. The organic electroluminescence device according to claim 11, wherein the light emitting layer comprises the compound according to claim 1.

15. The organic electroluminescence device according to claim 14, wherein the light emitting layer further comprises a heterocyclic derivative represented by general formula (N-1): ##STR00167## wherein X.sup.n1 to X.sup.n3 each independently represents CR.sup.n4 or N, R.sup.n1 to R.sup.n4 each independently represents hydrogen, halogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 25 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 cyclic atoms, a substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 25 carbon atoms, a substituted or unsubsituted arylthio group having 6 to 24 carbon atoms, alkyl or aryl substituted silyl group, alkyl or aryl substituted carbonyl group, or a substituted phosphoryl group, in the case of at least one of X.sup.n1 to X.sup.n3 represent CR.sup.n4, two or more substituents selected among R.sup.n1˜R.sup.n4 are optionally bonded to each other to form a ring structure.

Description

EXAMPLES

I Synthesis Examples

Synthesis Example 1: Compound 1

Synthesis Example 1-1

(1) ##STR00113##

(2) In a nitrogen flushed 1000 ml three-necked round-bottomed flask 4-bromo-2,5-difluoroaniline (20.5 g, 99 mmol) and 2-methoxyphenylboronic acid (17.97 g, 118 mmol) were dissolved in dimethoxyethane (200 ml) under nitrogen. 2M-sodium carbonate solution (99 ml, 197 mmol) and tetrakis(triphenylphosphine)palladium(0) (5.69 g, 4.93 mmol) were added to the reaction mixture. The reaction mixture was heated in an oil bath at 100° C. for 7 hours. Water was added to the reaction mixture followed by extraction with toluene. The combined organic layers were concentrated. The crude product was added to a silica gel column and was eluted with dichloromethane and hexane to give 25 g of white solid (quant, Intermediate 1). The identification of the intermediate 1 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 1-2

(3) ##STR00114##

(4) In a 1000 ml three-necked round-bottomed flask intermediate 1 (19.4 g, 82.4 mmol) was dissolved in acetone. 164 ml Hydrochloric acid (80 ml, 494 mmol) was added to the reaction mixture dropwise. Sodium nitrite (6.8 g, 99 mmol), as a solution in water (16 ml), was added to the reaction mixture dropwise. Potassium iodide (20.5 g, 124 mmol), as a solution in water (80 ml), was added to the reaction mixture dropwise. Water was added to the reaction mixture followed by extraction with toluene and then washed with 5% sodium sulfite solution. The combined organic layers were concentrated. The crude product was added to a silica gel column and was eluted with dichloromethane and hexane to give 14.4 g of white solid (86% yield, intermediate 2). The identification of the intermediate 2 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 1-3

(5) ##STR00115##

(6) In a dried 200 ml three-necked round-bottomed flask intermediate 2 (8.9 g, 25.7 mmol) and (5-chloro-2-methoxyphenyl)boronic acid (5.75 g, 30.9 mmol) were dissolved in dimethoxyethane (52 ml). Tetrakis(triphenylphosphine)palladium(0) (0.594 g, 0.514 mmol) and 2M-sodium carbonate solution (25.7 ml, 51.4 mmol), were added to the reaction mixture. The reaction mixture was heated in an oil bath at 100° C. for 7 hours. Water was added to the reaction mixture followed by extraction with toluene and then washed with water. The combined organic layers were concentrated. The crude product was added to a silica gel column and was eluted with toluene. The crude material was crystallized from ethyl acetate to give 5.3 g of white solid (57% yield, intermediate 3). The identification of the intermediate 3 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 1-4

(7) ##STR00116##

(8) In a nitrogen flushed 100 ml three-necked round-bottomed flask intermediate 3 (4.70 g, 13.03 mmol) was dissolved in dichloromethane under nitrogen. The reaction mixture was cooled to 0° C. with an ice/water bath. 1M-tribromoborane in dichloromethane (52.1 ml, 52.1 mmol) was added to the reaction mixture dropwise. The reaction mixture was heated to room temperature for 2 hours. The reaction mixture was cooled to 0° C. with an ice/water bath. Ice was added to the reaction mixture. The reaction mixture was filtered through a glass fiber paper and the filter cake was rinsed with water and dried to give 4.1 g of white solid (95% yield, intermediate 4). The identification of the intermediate 4 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 1-5

(9) ##STR00117##

(10) In a dried 200 ml three-necked round-bottomed flask intermediate 4 (2.78 g, 8.36 mmol) and potassium carbonate (3.46 g, 25.1 mmol) were dissolved in N-methyl-2-pyrrolidone (84 ml) under nitrogen. The reaction mixture was heated to 130° C. with an oil bath for 24 hours. The reaction mixture was added to water. The precipitation was rinsed with water and methanol and dried to give 2.0 g of white solid (82% yield, intermediate 5). The identification of the intermediate 5 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 1-6

(11) ##STR00118##

(12) The procedure of the synthesis of intermediate 1 was repeated except for using 3-bromocarbazole in place of 4-bromo-2,5-difluoroaniline and using 9-phenylcarbazole-3-yl boronic acid in place of 2-methoxyphenylboronic acid. The identification of the intermediate 6 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 1-7

(13) ##STR00119##

(14) In a nitrogen flushed 100 ml three-necked round-bottomed flask intermediate 6 (2.04 g, 5 mmol), intermediate 5 (1.61 g, 5.5 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.164 g, 0.4 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.092 g, 0.1 mmol) and sodium tert-butoxide (1.44 g, 15 mmol) were dissolved in xylene under nitrogen. The reaction mixture was heated 140° C. with an oil bath for 22 hours. The reaction mixture was filtered through a Buchner funnel and the filter cake was dissolved in dichloromethan. The crude product was added to a silica gel column and was eluted with dichloromethan and then washed with heated dioxane to give 1.88 g of white solid (57% yield, compound 1). The compound was measured for FD-MS (field desorption mass spectrometry), maximum ultraviolet absorption wavelength (UV(PhMe) λmax) in toluene, and maximum fluorescence wavelength (FL(PhMe, λex=300 nm) λmax) in toluene.

(15) The results are shown below.

(16) FDMS: calcd. for C48H28N202=664, found m/z=664 (M+)

(17) UV(PhMe) λmax: 341 nm

(18) FL(PhMe, λex=300 nm) λmax: 401 nm

Synthesis Example 2: Compound 2

Synthesis Example 2-1

(19) ##STR00120##

(20) The procedure of the synthesis of intermediate 1 was repeated except for using 1-bromo-2,4-dimethoxybenzene in place of 4-bromo-2,5-difluoroaniline and using 2-fluorophenylboronic acid in place of 2-methoxyphenylboronic acid. The identification of the intermediate 7 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 2-2

(21) ##STR00121##

(22) In a nitrogen flushed 300 ml three-necked round-bottomed flask intermediate 7 (15.0 g, 64.5 mmol) was dissolved in DMF (30 ml) under nitrogen. The reaction mixture was cooled to 0° C. with an ice/water bath. N-bromosuccinimide (11.2 g, 62.9 mmol), as a solution in DMF (30 ml), was added to the reaction mixture dropwise. The reaction mixture was heated to room temperature for 20 hours. Water was added to the reaction mixture followed by extraction with toluene. The combined organic layers were dried sodium sulfate, filtered and concentrated. The crude material was crystallized from acetone and methanol to give 14.8 g of white solid (73% yield). The identification of the intermediate 8 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 2-3

(23) ##STR00122##

(24) In a nitrogen flushed 500 ml three-necked round-bottomed flask intermediate 8 (14.8 g, 47.6 mmol), bis(pinacolato)diboron (24.2 g, 95 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (1.5 g, 3 mol %) and potassium acetate (14.0 g, 143 mmol) were dissolved in 1,4-dioxane (200 ml) under nitrogen. The reaction mixture was heated to 70° C. with an oil bath for 20 hours. Toluene was added to the reaction mixture followed by vacume concentration. The crude product was added to a silica gel column and was eluted with toluene to give 11.7 g of white solid (66% yield). The identification of the intermediate 9 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 2-4

(25) ##STR00123##

(26) The procedure of the synthesis of intermediate 1 was repeated except for using 4-bromo-1-fluoro-2-iodobenzene in place of 4-bromo-2,5-difluoroaniline and using intermediate 10 in place of 2-methoxyphenylboronic acid. The identification of the intermediate 11 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 2-5

(27) ##STR00124##

(28) The procedure of the synthesis of intermediate 4 was repeated except for using intermediate 11 in place of intermediate 3. The identification of the intermediate 12 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 2-6

(29) ##STR00125##

(30) The procedure of the synthesis of intermediate 5 was repeated except for using intermediate 12 in place of intermediate 4. The identification of the intermediate 13 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 2-7

(31) ##STR00126##

(32) The procedure of the synthesis of compound 1 was repeated except for using intermediate 13 in place of intermediate 5. The compound was measured for FD-MS (field desorption mass spectrometry), maximum ultraviolet absorption wavelength (UV(PhMe) λmax) in toluene, and maximum fluorescence wavelength (FL(PhMe, λex=300 nm) λmax) in toluene. The results are shown below.

(33) FDMS: calcd. for C48H28N202=664, found m/z=664 (M+)

(34) UV(PhMe) λmax: 335 nm

(35) FL(PhMe, λex=300 nm) λmax: 406 nm

Synthesis Example 3: Compound 3

Synthesis Example 3-1

(36) ##STR00127##

(37) The procedure of the synthesis of intermediate 1 was repeated except for using 2,3-difluoro-1,4-diiodobenzene in place of 4-bromo-2,5-difluoroaniline. The identification of the intermediate 14 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 3-2

(38) ##STR00128##

(39) The procedure of the synthesis of intermediate 8 was repeated except for using intermediate 7 in place of intermediate 8. The identification of the intermediate 15 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 3-3

(40) ##STR00129##

(41) The procedure of the synthesis of intermediate 1 was repeated except for using intermediate 15 in place of 4-bromo-2,5-difluoroaniline. The identification of the intermediate 16 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 3-4

(42) ##STR00130##

(43) The procedure of the synthesis of intermediate 4 was repeated except for using intermediate 16 in place of intermediate 3. The identification of the intermediate 17 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 3-5

(44) ##STR00131##

(45) The procedure of the synthesis of intermediate 5 was repeated except for using intermediate 17 in place of intermediate 4. The identification of the intermediate 18 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 3-6

(46) ##STR00132##

(47) The procedure of the synthesis of compound 1 was repeated except for using intermediate 18 in place of intermediate 5. The compound was measured for FD-MS (field desorption mass spectrometry), maximum ultraviolet absorption wavelength (UV(PhMe) λmax) in toluene, and maximum fluorescence wavelength (FL(PhMe, λex=300 nm) λmax) in toluene. The results are shown below.

(48) FDMS: calcd. for C48H28N202=664, found m/z=664 (M+)

(49) UV(PhMe) λmax: 319 nm

(50) FL(PhMe, λex=300 nm) λmax: 405 nm

Synthesis Example 4: Compound 4

Synthesis Example 4-1

(51) ##STR00133##

(52) In a nitrogen flushed 300 ml three-necked round-bottomed flask 3-fluorodibenzofuran (5.49 g, 29.5 mmol) was dissolved in tetrahydrofuran (58 ml) under nitrogen. The reaction mixture was cooled to −50° C. with a dry ice/acetone bath. n-Butyllithium solution 1.6 M in hexanes (18.4 ml, 29.5 mmol) was added to the reaction mixture. 1,2-Dibromoethane (8.31 g, 44.2 mmol) was added to the reaction mixture. The reaction mixture was heated to room temperature for 5 hours. Water and methanol were added to the reaction mixture followed by extraction with toluene. The reaction mixture was washed with brine. The combined organic layers were dried MgSO.sub.4, filtered and concentrated. The crude product was added to a silica gel column and was eluted with hexane to give 7.1 g of white solid (86% yield). The identification of the intermediate 19 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 4-2

(53) ##STR00134##

(54) The procedure of the synthesis of intermediate 1 was repeated except for using intermediate 19 in place of 4-bromo-2,5-difluoroaniline and using (2-chloro-5-methoxyphenyl)boronic acid in place of 2-methoxyphenylboronic acid. The identification of the intermediate 20 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 4-3

(55) ##STR00135##

(56) The procedure of the synthesis of intermediate 4 was repeated except for using intermediate 20 in place of intermediate 3. The identification of the intermediate 21 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 4-4

(57) ##STR00136##

(58) The procedure of the synthesis of intermediate 5 was repeated except for using intermediate 21 in place of intermediate 4. The identification of the intermediate 22 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 4-5

(59) ##STR00137##

(60) The procedure of the synthesis of compound 1 was repeated except for using intermediate 22 in place of intermediate 5. The compound was measured for FD-MS (field desorption mass spectrometry) and maximum fluorescence wavelength (FL(PhMe, λex=300 nm) λmax) in toluene. The results are shown below.

(61) FDMS: calcd. for C48H28N202=664, found m/z=664 (M+)

(62) FL(PhMe, λex=300 nm) λmax: 405 nm

Synthesis Example 5: Compound 5

Synthesis Example 5-1

(63) ##STR00138##

(64) The procedure of the synthesis of intermediate 1 was repeated except for using intermediate 19 in place of 4-bromo-2,5-difluoroaniline. The identification of the intermediate 23 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 5-2

(65) ##STR00139##

(66) The procedure of the synthesis of intermediate 4 was repeated except for using intermediate 23 in place of intermediate 3. The identification of the intermediate 24 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 5-3

(67) ##STR00140##

(68) The procedure of the synthesis of intermediate 5 was repeated except for using intermediate 24 in place of intermediate 4. The identification of the intermediate 25 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 5-4

(69) ##STR00141##

(70) The procedure of the synthesis of intermediate 8 was repeated except for using intermediate 25 in place of intermediate 7. The identification of the intermediate 26 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 5-5

(71) ##STR00142##

(72) The procedure of the synthesis of compound 1 was repeated except for using intermediate 26 in place of intermediate 5. The compound was measured for FD-MS (field desorption mass spectrometry) and maximum fluorescence wavelength (FL(PhMe, λex=300 nm) λmax) in toluene. The results are shown below.

(73) FDMS: calcd. for C48H28N202=664, found m/z=664 (M+)

(74) FL(PhMe, λex=300 nm) λmax: 403 nm

Synthesis Example 6: Compound 6

Synthesis Example 6-1

(75) ##STR00143##

(76) The procedure of the synthesis of intermediate 9 was repeated except for using intermediate 5 in place of intermediate 8. The identification of the intermediate 27 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 6-2

(77) ##STR00144##

(78) In a nitrogen flushed 350 ml three-necked round-bottomed flask intermediate 6 (5.72 g, 14 mmol), 1-bromo-3-fluorobenzene (14.7 g, 84 mmol), potassium phosphate tribasic (8.92 g, 42 mmol) in N-methyl-2-pyrrolidone(NMP) under nitrogen. The reaction mixture was heated 170° C. with an oil bath for 24 hours. The reaction mixture was cooled down and then precipitate salts were filtered. NMP was evaporated from the crude product. Ethanol was added to the crude product, the product precipitated, the product was washed with ethanol and water and dried under vacuum at 80° C. The product crystallized in 1-methoxy-2-proponol to give 5.02 of white solid (64% yield, intermediate 28). The identification of the intermediate 28 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 6-3

(79) ##STR00145##

(80) The procedure of the synthesis of intermediate 1 was repeated except for using intermediate 28 in place of 4-bromo-2,5-difluoroaniline and using intermediate 27 in place of 2-methoxyphenylboronic acid. The compound was measured for FD-MS (field desorption mass spectrometry) and maximum fluorescence wavelength (FL(PhMe, λex=350 nm) λmax) in toluene. The results are shown below.

(81) FDMS: calcd. for C54H32N202=740, found m/z=740 (M+)

(82) FL(PhMe, λex=350 nm) λmax: 405 nm

Synthesis Example 7: Compound 7

Synthesis Example 7-1

(83) ##STR00146##

(84) The procedure of the synthesis of intermediate 28 was repeated except for using 1-bromo-4-fluorobenzene in place of 1-bromo-3-fluorobenzene. The identification of the intermediate 29 was made by FD-MS (field desorption mass spectrometry) analysis.

Synthesis Example 7-2

(85) ##STR00147##

(86) The procedure of the synthesis of intermediate 1 was repeated except for using intermediate 29 in place of 4-bromo-2,5-difluoroaniline and using intermediate 27 in place of 2-methoxyphenylboronic acid. The compound was measured for FD-MS (field desorption mass spectrometry) and maximum fluorescence wavelength (FL(PhMe, λex=350 nm) λmax) in toluene. The results are shown below.

(87) FDMS: calcd. for C54H32N202=740, found m/z=740 (M+)

(88) FL(PhMe, λex=350 nm) λmax: 406 nm

II Application Examples

Application Example 1

(89) A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode was first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate was exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below were applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 Å/sec at about 10.sup.−8-10.sup.−8 mbar. As a hole injection layer, 5 nm-thick of compound HI was applied. Then 100 nm-thick of compound HT1 and 60 nm-thick compound HT2 were applied as hole transporting layer 1 and hole transporting layer 2, respectively. Subsequently, a mixture of 5% by weight of an emitter compound (tris[2-phenylpyridinato-C.sup.2,N]iridium(III), 47.5% by weight of a host (compound 1) and 47.5% by weight of compound PH1 were applied to form a 40 nm-thick phosphorescent-emitting layer. On the emitting layer, 30 nm-thick compound ET was applied as an electron transport layer. Finally, 1 nm-thick LiF was deposited as an electron injection layer and 80 nm-thick Al was then deposited as a cathode to complete the device. The device was sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen. To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristic was measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage (Voltage) is given at a current density of 10 mA/cm.sup.2. The device results are shown in Table 1.

(90) ##STR00148## ##STR00149##

Application Example 2-4 and Comparative Application Example 1-3

(91) Application Example 1 was repeated except for using each compound shown in Table 1 in place of the host (compound 1). The device results are shown in Table 1.

(92) TABLE-US-00001 TABLE 1 Appl. Ex. Host Voltage [V] CIE (x, y) Appl. Ex. 1 Compound 1 4.8 0.31, 0.63 Appl. Ex. 2 Compound 2 4.9 0.31, 0.63 Appl. Ex. 3 Compound 3 4.9 0.31, 0.63 Appl. Ex. 4 Compound 4 4.8 0.31, 0.63 Comp. Appl. Ex. 1 Comparative 5.2 0.31, 0.63 Compound 1 Comp. Appl. Ex. 2 Comparative 5.1 0.31, 0.63 Compound 2 Comp. Appl. Ex. 3 Comparative 5.7 0.31, 0.64 Compound 3 0

(93) The results shown in Table 1 demonstrate that the voltage is improved in the case that an inventive compound 1, 2, 3 and 4 are used as green hosts together with a co-host Compound PH1 in an OLED.

Application Example 5 and Comparative Application Example 4

(94) Application Example 1 or Comparative Application Example 1 was repeated except for using a host compound PH2 in place of the host (compound PH1). The device results are shown in Table 2.

(95) To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristic was measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage (Voltage) is given at a current density of 10 mA/cm.sup.2, and 80% lifetime (LT80), the time spent until the initial luminance at 50 mA/cm.sup.2 is reduced to 80%, is recorded. The device results are shown in Table 2.

(96) TABLE-US-00002 TABLE 2 Voltage LT80 Appl. Ex. Host [V] [hrs] CIE (x, y) Appl. Ex. 5 Compound 1 4.7 150 0.31, 0.63 Comp. Appl. Ex. Comparative Compound 5.2  80 0.31, 0.63 4 1

(97) The results shown in Table 2 demonstrate that the lifetime and voltage are improved in the case that an inventive compound 1 is used as a green host together with a co-host Compound PH2 in an OLED.

Application Examples 6, 7 and Comparative Application Example 5

(98) Application Example 5 was repeated except for using each compound shown in Table 3 in place of the host shown in Table 2. The device results are shown in Table 3.

(99) To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristic was measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). 80% lifetime (LT80), the time spent until the initial luminance at 50 mA/cm.sup.2 is reduced to 80%, is recorded. The device results are shown in Table 3.

(100) TABLE-US-00003 TABLE 3 Appl. Ex. Host LT80 [hrs] CIE (x, y) Appl. Ex. 6 Compound 6 140 0.31, 0.63 Appl. Ex. 7 Compound 7 150 0.31, 0.63 Comp. Appl. Ex. 5 Comparative Compound 4 100 0.31, 0.63