ORGANOELECTROLUMINESCENT DEVICE USING POLYCYCLIC AROMATIC DERIVATIVE COMPOUNDS

Abstract

An organoelectroluminescent device according to the present invention can achieve low-voltage driving and high-efficiency luminous characteristics with excellent external quantum efficiency by employing compounds having a characteristic structure as a hole transport material and a dopant material in a hole injection layer or hole transport layer and a light-emitting layer respectively, and thus can be effectively used in industrial applications such as flat display devices, flexible display devices, monochrome or white flat lighting devices, and monochrome or white flexible lighting devices.

Claims

1. An organic light-emitting device comprising: a first electrode; a second electrode facing the first electrode; and a hole injection layer or a hole transport layer and a light-emitting layer interposed between the first electrode and the second electrode, wherein (i) the hole injection layer or the hole transport layer comprises at least one compound represented by the following [Formula A], and (ii) the light-emitting layer comprises a compound represented by the following [Formula B] or [Formula C]: ##STR00248## wherein L is a single bond, a substituted or unsubstituted aromatic C6-C50 hydrocarbon ring, or a substituted or unsubstituted C2-C50 aromatic heterocyclic ring; n is an integer of 1 to 3, with the proviso that when n is 2 or more, L′s are identical to or different from each other; Ar is selected from a substituted or unsubstituted C5-C50 aryl group and a substituted or unsubstituted C2-C50 heteroaryl group; R.sub.a to R.sub.c are identical to or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-C30 arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a nitro group, a cyano group, and a halogen group, with the proviso that R.sub.b and R.sub.c are bonded to each other to further form an alicyclic or aromatic monocyclic or polycyclic ring, ##STR00249## wherein Q.sub.1 to Q.sub.3 are identical to or different from each other, and are each independently a substituted or unsubstituted aromatic C6-C50 hydrocarbon ring, or a substituted or unsubstituted C2-C50 aromatic heterocyclic group; Y.sub.1 to Y.sub.3 are identical to or different from each other, and are each independently selected from N-R.sub.1, CR.sub.2R.sub.3, O, S, Se, and SiR.sub.4R.sub.5; X is selected from B, P and P═O; and R.sub.1 to R.sub.5 are identical to or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-C30 arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a nitro group, a cyano group, and a halogen group, with the proviso that each of R.sub.1 to R.sub.5 is bonded to the ring Q.sub.1 to Q.sub.3 to further form an alicyclic or aromatic monocyclic or polycyclic ring, and R.sub.2 and R.sub.3, and R.sub.4 and R.sub.5 are bonded to each other to further form an alicyclic or aromatic monocyclic or polycyclic ring.

2. The organic light-emitting device according to claim 1, wherein [Formula B] or [Formula C] is represented by the following [Formula B-1] or [Formula C-1]: ##STR00250## wherein Z is CR or N, with the proviso that Z's and are identical to or different from each other and R′s are identical to or different from each other, wherein R's are each independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-C30 arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a nitro group, a cyano group, a halogen group and —N(R.sub.6)(R.sub.7), and R's are bonded to each other or each thereof is bonded to an adjacent substituent to form at least one alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atom of the formed alicyclic, aromatic monocyclic or polycyclic ring is substituted with at least one heteroatom selected from (N), a sulfur atom (S), and an oxygen atom (O), R.sub.6 and R.sub.7 are identical to or different from each other, and are each independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, and a substituted or unsubstituted C2-C50 heteroaryl group, with the proviso that R6 and R7 are bonded to each other to form an alicyclic or aromatic monocyclic or polycyclic ring, and X and Y.sub.1 to Y.sub.3 are as defined in [Formula B] and [Formula C] above.

3. The organic light-emitting device according to claim 1, wherein [Formula B] or [Formula C] is represented by any one of the following [Formula B-2], [Formula C-2] and [Formula D-2]: ##STR00251## wherein Z is CR or N, with the proviso that Z's are identical to or different from each other and R's are identical to or different from each other, wherein R's are identical to or different from each other and are each independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-C30 arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a nitro group, a cyano group, a halogen group and —N(R.sub.6)(R.sub.7), and R's are bonded to each other or each thereof is bonded to an adjacent substituent to form at least one alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atom of the formed alicyclic, aromatic monocyclic or polycyclic ring is substituted with at least one heteroatom selected from (N), a sulfur atom (S), and an oxygen atom (O), R.sub.6 and R.sub.7 are identical to or different from each other, and are each independently selected from hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, and a substituted or unsubstituted C2-C50 heteroaryl group, with the proviso that R.sub.6 and R.sub.7 are bonded to each other to form an alicyclic or aromatic monocyclic or polycyclic ring, and X and Y.sub.1 to Y.sub.3 are as defined in [Formula B] and [Formula C] above.

4. The organic light-emitting device according to claim 2, wherein at least one of R's is —N (R.sub.6) (R.sub.7).

5. The organic light-emitting device according to claim 3, wherein at least one of R's is —N (R.sub.6) (R.sub.7).

6. The organic light-emitting device according to claim 1, wherein L in [Formula A] is a single bond, or a substituted or unsubstituted aromatic C6-C50 hydrocarbon ring.

7. The organic light-emitting device according to claim 6, wherein L in [Formula A] is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted fluorenyl group.

8. The organic light-emitting device according to claim 1, wherein the compound represented by [Formula A] is selected from the compounds represented by the following formulas. ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275## ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285## ##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300## ##STR00301## ##STR00302## ##STR00303## ##STR00304## ##STR00305## ##STR00306## ##STR00307## ##STR00308## ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315##

9. The organic light-emitting device according to claim 1, wherein the compound represented by [Formula B] or [Formula C] is selected from the compounds represented by the following formulas: ##STR00316## ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346## ##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358##

10. The organic light-emitting device according to claim 1, further comprising at least one of a functional layer capable of injecting and/or transporting holes, an electron transport layer, an electron injection layer, a functional layer capable of transporting and injecting electrons, an electron blocking layer, a hole blocking layer and a hole auxiliary layer, in addition to the light-emitting layer, the hole injection layer and the hole transport layer.

11. The organic light-emitting device according to claim 10, wherein at least one selected from the layers is formed by a deposition process or a solution process.

12. The organic light-emitting device according to claim 1, wherein the organic light-emitting device is used for a display or lighting system selected from flat panel displays, flexible displays, monochromatic or white flat panel lighting systems, monochromatic or white flexible lighting systems, vehicle displays, and displays for virtual or augmented reality.

Description

MODE FOR INVENTION

[0067] Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, it will be obvious to those skilled in the art that these examples are merely provided for illustration of the present invention, and should not be construed as limiting the scope of the present invention.

[0068] <[Formula B] or [Formula C] Synthesis Example>

SYNTHESIS EXAMPLE 1

Synthesis of Compound 1

SYNTHESIS EXAMPLE 1-1

Synthesis of <Intermediate 1-a>

[0069] ##STR00194##

[0070] 50 g (423 mmol) of benzofuran and 500 mL of dichloromethane are added to a 1 L reactor, followed by stirring. The reaction product was cooled to -10° C., and a dilution of 67.7 g (423 mmol) of bromine in 100 mL of dichloromethane was added dropwise to the reaction product, followed by stirring at 0° C. for 2 hours. After completion of the reaction, an aqueous sodium thiosulfate solution was added thereto, followed by stirring and extraction with ethyl acetate and H2O. The organic layer was concentrated under reduced pressure and recrystallized with ethanol to obtain 100 g of <Intermediate 1-a>. (yield 93%)

SYNTHESIS EXAMPLE 1-2

Synthesis of <Intermediate 1-b>

[0071] <Intermediate 1-b> was synthesized by the following [Reaction Scheme 2].

##STR00195##

[0072] 48.6 g (866 mmol) of potassium hydroxide was dissolved in 400 mL of ethanol in a 1L reactor. A solution of 120 g (433 mmol) of <Intermediate 1-A> in ethanol was added dropwise thereto at 0° C., followed by stirring under reflux for 2 hours. After completion of the reaction, the ethanol organic layer was concentrated under reduced pressure and extracted with ethyl acetate and water. The result was separated by column chromatography to obtain 42 g of <intermediate 1-b>. (yield 50%)

SYNTHESIS EXAMPLE 1-3

Synthesis of <Intermediate 1-c>

[0073] <Intermediate 1-c> was synthesized by the following [Reaction Scheme 3].

##STR00196##

[0074] 4.5 g (16 mmol) of 1-bromo-3-iodobenzene, 5.8 g (16 mmol) of aniline, 0.1 g (1 mmol) of palladium acetate, 3 g (32 mmol) of sodium tert-butoxide, 0.2 g (1 mmol) of bis(diphenylphosphino)-1,1′-binaphthyl and 45 mL of toluene were added to a 100 mL reactor, followed by stirring under reflux for 24 hours. After completion of the reaction, the product was filtered and the filtrate was concentrated and separated by column chromatography to obtain 5.2 g of <Intermediate 1-c>. (yield 82%)

SYNTHESIS EXAMPLE 1-4

Synthesis of <Intermediate 1-d>

[0075] <Intermediate 1-d> was synthesized by the following [Reaction Scheme 4].

##STR00197##

[0076] 20 g (98 mmol) of <Intermediate 1-c>, 18.4 g (98 mmol) of <Intermediate 1-b>, 0.5 g (2 mmol) of palladium acetate, 18.9 g (196 mmol) of sodium tert-butoxide, 0.8 g (4 mmol) of tri-tert-butylphosphine, and 200 mL of toluene were added to a 250 mL reactor, followed by stirring under reflux for 5 hours. After completion of the reaction, the product was filtered and the filtrate was concentrated and separated by column chromatography to obtain 22 g of <Intermediate 1-d>. (yield 75%)

SYNTHESIS EXAMPLE 1-5

Synthesis of <Intermediate 1-e>

[0077] <Intermediate 1-e> was synthesized by the following [Reaction Scheme 5].

##STR00198##

[0078] 18.5 g of <Intermediate 1-e> was obtained in the same manner as in Synthesis Example 1-3, except that <Intermediate 1-d> was used instead of 1-bromo-4-iodobenzene. (yield 74.1%)

SYNTHESIS EXAMPLE 1-6

Synthesis of <Intermediate 1-f>

[0079] <Intermediate 1-f> was synthesized by the following [Reaction Scheme 6].

##STR00199##

[0080] 12 g of <Intermediate 1-f> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 1-e> and 1-bromo-2-iodobenzene were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 84.1%)

SYNTHESIS EXAMPLE 1-7

Synthesis of <Compound 1>

[0081] <Compound 1> was synthesized by the following [Reaction Scheme 7].

##STR00200##

[0082] 12 g (23 mmol) of <Intermediate 1-f> and 120 mL of tert-butylbenzene were added to a 300 mL reactor. 42.5 mL (68 mmol) of n-butyllithium was added dropwise thereto at −78° C. Then, the mixture was stirred at 60° C. for 3 hours. Then, the heptane was removed by purging with nitrogen at 60° C. 11.3 g (45 mmol) of boron tribromide was added dropwise at -78° C. Then, the mixture was stirred at room temperature for 1 hour, and 5.9 g (45 mmol) of N,N-diisopropylethylamine was added dropwise at 0° C. Then, the mixture was stirred at 120° C. for 2 hours. After completion of the reaction, a sodium acetate solution was added thereto at room temperature, followed by stirring. The result was extracted with ethyl acetate, and the organic layer was concentrated and separated by column chromatography to obtain 0.8 g of <Compound 1>. (yield 13%)

[0083] MS (MALDI-TOF): m/z 460.17 [Mt]

SYNTHESIS EXAMPLE 2

Synthesis of Compound 2

SYNTHESIS EXAMPLE 2-1

Synthesis of <Intermediate 2-a>

[0084] <Intermediate 2-a> was synthesized by the following [Reaction Scheme 8].

##STR00201##

[0085] 50 g (373 mmol) of benzothiophene and 500 mL of dichloromethane are added to a 1 L reactor, followed by stirring. The reaction product was cooled to −0° C., and a dilution of 59.5 g (373 mmol) of bromine in 100 mL of chloroform was added dropwise to the reaction product, followed by stirring at room temperature for 4 hours. After completion of the reaction, an aqueous sodium thiosulfate solution was added thereto, followed by stirring and extraction with ethyl acetate and H.sub.2O. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 70 g of <Intermediate 2-a>. (yield 91%)

Synthesis Example 2-2

Synthesis of <Intermediate 2-b>

[0086] <Intermediate 2-b> Was synthesized by the following [Reaction Scheme 9].

##STR00202##

[0087] 32 g of <Intermediate 2-b> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 2-a> was used instead of <Intermediate 1-b>. (yield 75.4%)

SYNTHESIS EXAMPLE 2-3

Synthesis of <Intermediate 2-c>

[0088] <Intermediate 2-c> was synthesized by the following [Reaction Scheme 10].

##STR00203##

[0089] 24.5 g of <Intermediate 2-c> was obtained in the same manner as in Synthesis Example 1-3, except that <Intermediate 2-b> was used instead of 1-bromo-4-iodobenzene. (yield 73.1%)

SYNTHESIS EXAMPLE 2-4

Synthesis of <Intermediate 2-d>

[0090] <Intermediate 2-d> was synthesized by the following [Reaction Scheme 11].

##STR00204##

[0091] 21 g of <Intermediate 2-d> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 2-c> and 1-bromo-2-iodobenzene were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 77.5%)

SYNTHESIS EXAMPLE 2-5

Synthesis of <Compound 2>

[0092] <Compound 2> was synthesized by the following [Reaction Scheme 12].

##STR00205##

[0093] 1.5 g of <Compound 2> was obtained in the same manner as in Synthesis Example 1-7, except that <Intermediate 2-d>was used instead of <Intermediate 1-f>. (yield 10.1%)

[0094] MS (MALDI-TOF): m/z 467.15 [Mt]

SYNTHESIS EXAMPLE 3

Synthesis of Compound 13

SYNTHESIS EXAMPLE 3-1

Synthesis of <Intermediate 3-a>

[0095] <Intermediate 3-a> was synthesized by the following [Reaction Scheme 13].

##STR00206##

[0096] 50 g (177 mmol) of 1-bromo-3(tert-butyl)-5-iodobenzene, 36.2 g (389 mmol) of aniline, 1.6 g (7 mmol) of palladium acetate, 51 g (530 mmol) of sodium tert-butoxide, 4.4 g (7 mmol) of bis(diphenylphosphino)-1,1′-binaphthyl, and 500 mL of toluene were added to a 1L reactor, followed by stirring under reflux for 24 hours. After completion of the reaction, the reaction product was filtered. The filtrate was concentrated and separated by column chromatography to obtain 42.5 g of <Intermediate 3-a>. (yield 50%)

SYNTHESIS EXAMPLE 3-2

Synthesis of <Intermediate 3-b>

[0097] <Intermediate 3-b> was synthesized by the following [Reaction Scheme 14].

##STR00207##

[0098] 11 g (42 mmol) of <Intermediate 3-a>, 20 g (101 mmol) of <Intermediate 1-b>, 1 g (2 mmol) of palladium acetate, 12.2 g (127 mmol) of sodium tert-butoxide, 0.7 g (3 mmol) of tri-tert-butylphosphine and 150 mL of toluene were added to a 250 mL reactor, followed by stirring under reflux for 5 hours. After completion of the reaction, the reaction product was filtered and the filtrate was concentrated and then separated by column chromatography to obtain 11 g of <Intermediate 3-b>. (yield 65%)

SYNTHESIS EXAMPLE 3-3

Synthesis of <Compound 13>

[0099] <Compound 13> was synthesized by the following [Reaction Scheme 15].

##STR00208##

[0100] 0.5 g of <Compound 13> was obtained in the same manner as in Synthesis Example 1-7, except that <Intermediate 3-b>was used instead of <Intermediate 1-f>. (yield 8%)

[0101] MS (MALDI-TOF): m/z 556.23 [Mt]

SYNTHESIS EXAMPLE 4

Synthesis of Compound 65

SYNTHESIS EXAMPLE 4-1

Synthesis of <Intermediate 4-a>

[0102] <Intermediate 4-a> was synthesized by the following [Reaction Scheme 16].

##STR00209##

[0103] 35.6 g of <Intermediate 4-a> was obtained in the same manner as in Synthesis Example 1-3, except that 1-bromo-2,3-dichlorobenzene was used instead of 1-bromo-4-iodobenzene. (yield 71.2%)

SYNTHESIS EXAMPLE 4-2

Synthesis of <Intermediate 4-b>

[0104] <Intermediate 4-b> was synthesized by the following [Reaction Scheme 17].

##STR00210##

[0105] 60.0 g (355 mmol) of diphenylamine, 100.3 g (355 mmol) of 1-bromo-3-iodobenzene, 0.8 g (4 mmol) of palladium acetate, 2 g (4 mmol) of xantphos, 68.2 g (709 mmol) of sodium tertiary butoxide, and 700 mL of toluene were added to a 2 L reactor, followed by stirring under reflux for 2 hours. After completion of the reaction, the resulting product was filtered at room temperature, concentrated under reduced pressure, and separated by column chromatography to obtain 97 g of <Intermediate 4-b>. (yield 91.2%)

SYNTHESIS EXAMPLE 4-3

Synthesis of <Intermediate 4-c>

[0106] <Intermediate 4-c> was synthesized by the following [Reaction Scheme 18].

##STR00211##

[0107] 31 g of <Intermediate 4-c> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 4-a> and <Intermediate 4-b> were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 77.7%)

SYNTHESIS EXAMPLE 4-4

Synthesis of <Intermediate 4-d>

[0108] <Intermediate 4-d> was synthesized by the following [Reaction Scheme 19].

##STR00212##

[0109] 30 g (174 mmol) of 3-bromoaniline, 25.5 g (209 mmol) of phenylboronic acid, 4 g (3 mmol) of tetrakis(triphenylphosphine)palladium, 48.2 g (349 mmol) of potassium carbonate, 150 mL of 1,4-dioxane, 150 mL of toluene, and 90 mL of distilled water were added to a 1 L reactor, followed by stirring under reflux for 4 hours. After completion of the reaction, the layers were separated at room temperature, and the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 24 g of <Intermediate 4-d>. (yield 80%)

SYNTHESIS EXAMPLE 4-5

Synthesis of <Intermediate 4-e>

[0110] <Intermediate 4-e> was synthesized by the following [Reaction Scheme 20].

##STR00213##

[0111] 31.6 g of <Intermediate 4-e> was obtained in the same manner as in Synthesis Example 1-3, except that <Intermediate 4-d> and <Intermediate 1-b> were used instead of 1-bromo-4-iodobenzene and aniline. (yield 68.2%)

SYNTHESIS EXAMPLE 4-6

Synthesis of <Intermediate 4-f>

[0112] <Intermediate 4-f> was synthesized by the following [Reaction Scheme 21].

##STR00214##

[0113] 21 g of <Intermediate 4-f> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 4-c> and <Intermediate 4-e> were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 67.7%)

SYNTHESIS EXAMPLE 4-7

Synthesis of <Compound 65>

[0114] <Compound 65> was synthesized by the following [Reaction Scheme 22].

##STR00215##

[0115] 21 g (37 mmol) of <Intermediate 4-f> and tert-butylbenzene were added to a 250 mL reactor. 42.4 mL (74 mmol) of n-butyllithium was added dropwise thereto at −78° C.

[0116] Then, the mixture was stirred at 60° C. for 3 hours. Then, the pentane was removed at 60° C. by nitrogen purging. 7.1 mL (74 mmol) of boron tribromide was added dropwise at −78° C. Then, the mixture was stirred at room temperature for 1 hour, and 6 g (74 mmol) of N,N-diisopropylethylamine was added dropwise at 0° C. Then, the mixture was stirred at 120° C. for 2 hours. After completion of the reaction, a sodium acetate solution was added thereto at room temperature, followed by stirring. The result was extracted with ethyl acetate, and the organic layer was concentrated and separated by column chromatography to obtain 2.0 g of <Compound 65>. (yield 17.4%)

[0117] MS (MALDI-TOF): m/z 703.28 [Mt]

SYNTHESIS EXAMPLE 5

Synthesis of Compound 73

[0118] Synthesis Example 5-1. Synthesis of <Intermediate 5-a>

[0119] <Intermediate 5-a> was synthesized by the following [Reaction Scheme 23].

##STR00216##

[0120] 40 g (236 mmol) of 4-tert-butylaniline was dissolved in 400 mL of methylene chloride in a 1 L reactor, followed by stirring at 0° C. Then, 42 g (236 mmol) of N-bromosuccinimide was slowly added to the reactor. The reaction product was warmed to room temperature and was stirred for 4 hours. After completion of the reaction, H.sub.2O was added dropwise thereto at room temperature and extracted with methylene chloride. The organic layer was concentrated and separated by column chromatography to obtain 48 g of <Intermediate 5-a> (yield 80%).

SYNTHESIS EXAMPLE 5-2

Synthesis of <Intermediate 5-b>

[0121] <Intermediate 5-b> was synthesized by the following [Reaction Scheme 24].

##STR00217##

[0122] 80 g (351 mmol) of <Intermediate 5-a> and 450 mL of water are added to a 2 L reactor, followed by stirring. 104 mL of sulfuric acid was further added thereto. A solution of 31.5 g (456 mmol) of sodium nitrite in 240 mL of water was added dropwise thereto at 0° C. Then, the mixture was stirred at 0° C. for 2 hours. A solution of 116.4 g (701 mmol) of potassium iodide in 450 mL of water was added dropwise at 0° C. Then, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, an aqueous sodium thiosulfate solution was added thereto at room temperature, followed by stirring. The reaction product was extracted with ethyl acetate and the organic layer was concentrated and separated by column chromatography to obtain 58 g of <Intermediate 5-b>. (yield 51%)

SYNTHESIS EXAMPLE 5-3

Synthesis of <Intermediate 5-c>

[0123] <Intermediate 5-c> was synthesized by the following [Reaction Scheme 25].

##STR00218##

[0124] 95 g of <Intermediate 4-c> was obtained in the same manner as in Synthesis Example 3-1, except that 4-tert-butylaniline was used instead of aniline. (yield 80.4%)

SYNTHESIS EXAMPLE 5-4

Synthesis of <Intermediate 5-d>

[0125] <Intermediate 5-d> was synthesized by the following [Reaction Scheme 26].

##STR00219##

[0126] 31 g of <Intermediate 5-d> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 5-c> was used instead of <Intermediate 1-c>. (yield 71.5%)

Synthesis Example 5-5

Synthesis of <Intermediate 5-e>

[0127] <Intermediate 5-e> was synthesized by the following [Reaction Scheme 27].

##STR00220##

[0128] 24 g of <Intermediate 5-e> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 5-d> and <Intermediate 5-b> were used instead of <Intermediate 1-c> and <Intermediate 1-b> (yield 67.1%)

SYNTHESIS EXAMPLE 5-6

Synthesis of <Compound 73>

[0129] <Compound 73> was synthesized by the following [Reaction Scheme 28].

##STR00221##

[0130] 2.4 g of <Compound 73> was obtained in the same manner as in Synthesis Example 1-7, except that <Intermediate 5-e>was used instead of <Intermediate 1-f>. (yield 15%)

[0131] MS (MALDI-TOF): m/z 628.36 [Mt]

SYNTHESIS EXAMPLE 6

Synthesis of Compound 109

Synthesis Example 6-1

Synthesis of <Intermediate 6-a>

[0132] <Intermediate 6-a> was synthesized by the following [Reaction Scheme 29].

##STR00222##

[0133] 40.0 g (123 mmol) of 1,5-dichloro-2,4-dinitrobenzene, 44.9 g (368 mmol) of phenylboronic acid, 2.8 g (2.5 mmol) of tetrakis(triphenylphosphine) palladium, 50.9 g (368 mmol) of potassium carbonate, 120 mL of 1,4-dioxane, 200 mL of toluene and 120 mL of water were added to a 1 L reactor, followed by stirring under reflux. After completion of the reaction, the reaction product was extracted with water and ethyl acetate and the organic layer was concentrated and separated by column chromatography to obtain 27.5 g of <Intermediate 6-a>. (yield

SYNTHESIS EXAMPLE 6-2

Synthesis of <Intermediate 6-b>

[0134] <Intermediate 6-b> was synthesized by the following [Reaction Scheme 30].

##STR00223##

[0135] 27.5 g (86 mmol) of <Intermediate 6-a>, 57.8 g (348 mmol) of triphenylphosphine, and 300 mL of dichlorobenzene were added to a 1 L reactor, followed by stirring under reflux for 3 days. After completion of the reaction, the dichlorobenzene was removed and the residue was separated by column chromatography to obtain 10.8 g of <Intermediate 6-b>. (yield 49.0%)

SYNTHESIS EXAMPLE 6-3

Synthesis of <Intermediate 6-c>

[0136] <Intermediate 6-c> was synthesized by the following [Reaction Scheme 31].

##STR00224##

[0137] 10.8 g (42 mmol) of <Intermediate 6-b>, 11.0 g (10.8 mmol) of <Intermediate 2-a>, 10.7 g (1 mmol) of a copper powder, 4.5 g (17 mmol) of 18-crown-6-ether, 34.9 g (253 mmol) of potassium carbonate, and 110 mL of dichlorobenzene were added to a 250 mL reactor, followed by stirring under reflux at 180° C. for 24 hours. After completion of the reaction, the dichlorobenzene was removed and the residue was separated by column chromatography to obtain 9.5 g of <Intermediate 6-c>. (yield 52%)

SYNTHESIS EXAMPLE 6-4

Synthesis of <Intermediate 6-d>

[0138] <Intermediate 6-d> was synthesized by the following [Reaction Scheme 32].

##STR00225##

[0139] 14 g of <Intermediate 6-d> was obtained in the same manner as in Synthesis Example 6-3, except that <Intermediate 6-c> and 1-bromo-2-iodobenzene were used instead of <Intermediate 1-c> and <Intermediate 2-a> (yield 67.1%)

SYNTHESIS EXAMPLE 6-5

Synthesis of <Compound 109>

[0140] <Compound 109> was synthesized by the following [Reaction Scheme 33].

##STR00226##

[0141] 2.1 g of <Compound 109> was obtained in the same manner as in Synthesis Example 1-7, except that <Intermediate 6-d> was used instead of <Intermediate 1-f> (yield 14%)

[0142] MS (MALDI-TOF): m/z 472.12 [Mt]

SYNTHESIS EXAMPLE 7

Synthesis of Compound 126

SYNTHESIS EXAMPLE 7-1

Synthesis of <Intermediate 7-a>

[0143] <Intermediate 7-a> was synthesized by the following [Reaction Scheme 34].

##STR00227##

[0144] 30.0 g (150 mmol) of <Intermediate 2-b>, 31.2 g (160 mmol) of phenol, 45.7 g (300 mmol) of potassium carbonate and 250 mL of NMP were added to a 500 mL reactor, followed by stirring under reflux at 160° C. for 12 hours. After completion of the reaction, the reaction product was cooled to room temperature, the NMP was distilled off under reduced pressure and the residue was extracted with water and ethyl acetate. The solvent was concentrated under reduced pressure and separated by column chromatography to obtain 22 g of <Intermediate 7-a>. (yield 68%)

SYNTHESIS EXAMPLE 7-2

Synthesis of <Compound 126>

[0145] <Compound 126> was synthesized by the following [Reaction Scheme 35].

##STR00228##

[0146] 1.2 g of <Compound 126> was obtained in the same manner as in Synthesis Example 1-7, except that <Intermediate 7-a>was used instead of <Intermediate 1-f> (yield 13.4%)

[0147] MS (MALDI-TOF): m/z 401.10 [Mt]

SYNTHESIS EXAMPLE 8

Synthesis of Compound 145

SYNTHESIS EXAMPLE 8-1

Synthesis of <Intermediate 8-a>

[0148] <Intermediate 8-a> was synthesized by the following [Reaction Scheme 36].

##STR00229##

[0149] 41.6 g of <Intermediate 8-a> was obtained in the same manner as in Synthesis Example 1-3, except that 2-bromo tert-butyl-1,3-dimethylbenzene and 4-tert-butylaniline were used instead of 1-bromo-3-iodobenzene and aniline (yield 88.2%)

Synthesis Example 8-2

Synthesis of <Intermediate 8-b>

[0150] <Intermediate 8-b> was synthesized by the following [Reaction Scheme 37].

##STR00230##

[0151] 37.6 g of <Intermediate 8-b> was obtained in the same manner as in Synthesis Example 4-2, except that <Intermediate 8-a> was used instead of diphenylamine. (yield 78.4%)

SYNTHESIS EXAMPLE 8-3

Synthesis of <Intermediate 8-c>

[0152] <Intermediate 8-c> was synthesized by the following [Reaction Scheme 38].

##STR00231##

[0153] 31.2 g of <Intermediate 8-c> was obtained in the same manner as in Synthesis Example 1-3, except that <Intermediate 8-b> and 4-tert-butylaniline were used instead of 1-bromo-3-iodobenzene and aniline. (yield 74.2%)

SYNTHESIS EXAMPLE 8-4

Synthesis of <Intermediate 8-d>

[0154] <Intermediate 8-d> was synthesized by the following [Reaction Scheme 39].

##STR00232##

[0155] 30.3 g of <Intermediate 8-d> was obtained in the same manner as in Synthesis Example 1-3, except that 1-bromo-2,3-dichloro-5-ethylbenzene and 4-tert-butylaniline were used instead of 1-bromo-3-iodobenzene and aniline. (yield 89.8%)

Synthesis Example 8-5

Synthesis of <Intermediate 8-e>

[0156] <Intermediate 8-e> was synthesized by the following [Reaction Scheme 40].

##STR00233##

[0157] 27.4 g of <Intermediate 8-e> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 8-d> and 3-bromo-5-(tert-butyl)benzothiophene were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 77.1%)

Synthesis Example 8-6

Synthesis of <Intermediate 8-f>

[0158] <Intermediate 8-f> was synthesized by the following [Reaction Scheme 41].

##STR00234##

[0159] 21 g of <Intermediate 8-f> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 8-e> and <Intermediate 8-c> were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 74.1%)

Synthesis Example 8-7

Synthesis of <Compound 145>

[0160] <Compound 145> was synthesized by the following [Reaction Scheme 42].

##STR00235##

[0161] 3.4 g of <Compound 145> was obtained in the same manner as in Synthesis Example 1-7, except that <Intermediate 8-f>was used instead of <Intermediate 1-f>. (yield 19.4%)

[0162] MS [M].sup.+979.60

SYNTHESIS EXAMPLE 9

Synthesis of Compound 150

SYNTHESIS EXAMPLE 9-1

Synthesis of <Intermediate 9-a>

[0163] <Intermediate 9-a> was synthesized by the following [Reaction Scheme 43].

##STR00236##

[0164] 32.7 g of <Intermediate 9-a> was obtained in the same manner as in Synthesis Example 1-3, except that bromobenzene-d5 and 4-tert-butylaniline were used instead of 1-bromo iodobenzene and aniline. (yield 78.2%)

SYNTHESIS EXAMPLE 9-2

Synthesis of <Intermediate 9-b>

[0165] <Intermediate 9-b> was synthesized by the following [Reaction Scheme 44].

##STR00237##

[0166] 34.2 g of <Intermediate 9-b> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 8-e> and <Intermediate 9-a> were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 84.1%)

SYNTHESIS EXAMPLE 9-3

Synthesis of <Compound 150>

[0167] <Compound 150> was synthesized by the following [Reaction Scheme 45].

##STR00238##

[0168] 2.7 g of <Compound 150> was obtained in the same manner as in Synthesis Example 1-7, except that <Intermediate 9-b> was used instead of <Intermediate 1-f>. (yield 11.4%)

[0169] MS [M].sup.+663.39

SYNTHESIS EXAMPLE 10

Synthesis of Compound 153

SYNTHESIS EXAMPLE 10-1

Synthesis of <Intermediate 10-a>

[0170] <Intermediate 10-a> was synthesized by the following [Reaction Scheme 46].

##STR00239##

[0171] 25.6 g of <Intermediate 10-a> was obtained in the same manner as in Synthesis Example 1-3, except that 1-bromo-dibenzofuran and 4-tert-butylaniline were used instead of 1-bromo-3-iodobenzene and aniline. (yield 79.2%)

SYNTHESIS EXAMPLE 10-2

Synthesis of <Intermediate 10-b>

[0172] <Intermediate 10-b> was synthesized by the following [Reaction Scheme 47].

##STR00240##

[0173] 18.6 g of <Intermediate 10-b> was obtained in the same manner as in Synthesis Example 1-4, except that <Intermediate 8-e> and <Intermediate 10-a> were used instead of <Intermediate 1-c> and <Intermediate 1-b>. (yield 74.1%)

SYNTHESIS EXAMPLE 10-3

Synthesis of <Compound 153>

[0174] <Compound 153> was synthesized by the following [Reaction Scheme 48].

##STR00241##

[0175] 3.4 g of <Compound 153> was obtained in the same manner as in Synthesis Example 1-7, except that <Intermediate 10-b> was used instead of <Intermediate 1-f>. (yield 15.4%)

[0176] MS [M].sup.+748.37

[0177] <[Formula A] Synthesis Example>

SYNTHESIS EXAMPLE 11

Synthesis of Compound 12

SYNTHESIS EXAMPLE 11-1

Synthesis of <Intermediate 11-a>

[0178] ##STR00242##

[0179] 3-bromo-9-phenyl-9H-carbazole (11.3 g, 0.035 mol), 4-aminobiphenyl (6.6 g, 0.039 mol), tris(dibenzylideneacetone)dipalladium (0) (0.65 g, 0.0007 mol), sodium tert-butoxide (6.79 g, 0.0706 mol), 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (0.44 g, 0.0007 mol) and 100 mL of toluene were added to a round-bottom flask, followed by stirring under reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated, dehydrated with magnesium sulfate, and then concentrated under reduced pressure. The result was separated by column chromatography to obtain 12.2 g of <Intermediate 11-a>. (yield 85%)

SYNTHESIS EXAMPLE 11-2

Synthesis of <Compound 12>

[0180] ##STR00243##

[0181] 3-bromo-9,9-dimethylfluorene (2.4 g, 0.009 mol), <Intermediate 11-a> (5.3 g, 0.013 mol), palladium (II) acetate (0.08 g, 0.4 mmol), sodium tert-butoxide (3.4 g, 0.035 mol), tritert-butylphosphine (0.07 g, 0.4 mmol), and 60 mL of toluene were added to a round-bottom flask, followed by stirring under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was separated, dehydrated with magnesium sulfate, and then concentrated under reduced pressure. The result was separated and purified by column chromatography and recrystallized with dichloromethane and acetone to obtain 2.6 g of <Compound 12>. (yield 48%)

[0182] MS (MALDI-TOF): m/z 602.27 [Mt]

SYNTHESIS EXAMPLE 12

Synthesis of Compound 30

SYNTHESIS EXAMPLE 12-(1)

Synthesis of Compound 30

[0183] <Compound 30> was synthesized in the same manner as in Synthesis Example 5 except that 1-naphthylamine was used instead of 4-aminobiphenyl used in Synthesis Example 5-(1), and 3-bromo-9,9-dimethylfluorene was used instead of 2-bromo-9,9-dimethylfluorene used in Synthesis Example 5-(2) (yield 45%).

[0184] MS (MALDI-TOF): m/z 830.29 [Mt]

SYNTHESIS EXAMPLE 13

Synthesis of Compound 44

SYNTHESIS EXAMPLE 13-(1)

Synthesis of Compound 44

[0185] <Compound 44> was synthesized in the same manner as in Synthesis Example 5 except that aniline-2,3,4,5,6-d5 was used instead of 4-aminobiphenyl used in Synthesis Example 5-(1), and 2-bromo-9,9′-dimethylfluorene was used instead of 2-bromo-9,9-dimethylfluorene used in Synthesis Example 5-(2) (yield 46%).

[0186] MS (MALDI-TOF): m/z 653.29 [Mt]

SYNTHESIS EXAMPLE 14

Synthesis of Compound 78

Synthesis Example 14-(1): Synthesis of Compound 78

[0187] <Compound 78> was synthesized in the same manner as in Synthesis Example 5 except that 2-bromo-9,9-diphenylfluorene was used instead of 2-bromo-9,9-dimethylfluorene used in Synthesis Example 5-(2) (yield 46%).

[0188] MS (MALDI-TOF): m/z 726.30 [Mt]

SYNTHESIS EXAMPLE 15

Synthesis of Compound 102

[0189] Synthesis Example 15-(1): Synthesis of Compound 102 <Compound 102> was synthesized in the same manner as in Synthesis Example 5, except that 2-naphthylamine was used instead of 4-aminobiphenyl used in Synthesis Example 5-(1) and 2-(4-bromophenyl)-9,9-diphenyl-9H-fluorene was used instead of 2-bromo-9,9-dimethylfluorene used in Synthesis Example 5-(2) (yield 45%).

[0190] MS (MALDI-TOF): m/z 776.32 [M.sup.+]

SYNTHESIS EXAMPLE 16

Synthesis of Compound 174

SYNTHESIS EXAMPLE 16-(1)

Synthesis of Compound 174

[0191] <Compound 174> was synthesized in the same manner as in Synthesis Example 5, except that 3-bromo-9-phenyl-9H-carbazole was used instead of 2-bromo-9-phenyl-9H-carbazole used in Synthesis Example 5-(1), and 4-(1-naphthyl)aniline was used instead of 4-aminobiphenyl (yield 47%).

[0192] MS (MALDI-TOF): m/z 652.29 [M.sup.+]

SYNTHESIS EXAMPLE 17

Synthesis of Compound 195

SYNTHESIS EXAMPLE 17-(1)

Synthesis of Compound 195

[0193] <Compound 195> was synthesized in the same manner as in Synthesis Example 5, except that 3-bromo-9-phenyl-9H-carbazole was used instead of 2-bromo-9-phenyl-9H-carbazole used in Synthesis Example 5-(1), 3-aminobiphenyl was used instead of 4-aminobiphenyl, and 1-(4-bromophenyl)-9,9-dimethyl-9H-fluorene was used instead of 2-bromo-9,9-dimethylfluorene used in Synthesis Example 5-(2). (yield 45%)

[0194] MS (MALDI-TOF): m/z 678.30 [Mt]

EXAMPLES 1 to 21

Fabrication of Organic Light-Emitting Devices

[0195] ITO glass was patterned such that a light-emitting area of the ITO glass was adjusted to 2 mm×2 mm and was then washed. The ITO glass was mounted in a vacuum chamber, a base pressure was set to 1×10.sup.−7 torr, and 2-TNATA (400Å) and a material for a hole transport layer shown in [Table 1] (200 Å) were sequentially deposited on the ITO glass. Then, a mixture of [BH] as a host and the compound shown in the following Table 1 as a dopant (3 wt %) was deposited to a thickness of 250Å to form a light-emitting layer. Then, a compound of [Formula E-1] was deposited thereon to a thickness of 300Å to form an electron transport layer, Liq was deposited thereon to a thickness of 10Å to form an electron injection layer, and Al was deposited thereon to a thickness of 1,000Å to form a cathode. As a result, an organic light-emitting device was fabricated. The properties of the organic light-emitting device were measured at 10 mA/cm.sup.2.

##STR00244##

Comparative Examples 1 to 6

[0196] Organic light-emitting devices were fabricated in the same manner as in Examples above, except that [HT], and [BD1] and [BD2] were used instead of the compound used as the hole transport layer material and dopant compounds, respectively, in Examples 1 to 16. The properties of the organic light-emitting devices were measured at 10 mA/cm.sup.2. The structures of [HT], [BD1] and [BD2] are as follows.

TABLE-US-00001 TABLE l [HT] [00245] [BD1] [00246] [BD2] [00247] Hole Light-emitting transport layer layer (dopant) Voltage External quantum Item [Formula A] [Formula B/C] (V) efficiency (%) Example 1 12 1 3.6 11.1 Example 2 44 1 3.5 11.5 Example 3 102 1 3.6 11.2 Example 4 174 1 3.6 10.9 Example 5 30 2 3.6 10.8 Example 6 44 2 3.5 11.5 Example 7 78 2 3.5 11.7 Example 8 195 2 3.6 11.2 Example 9 30 13 3.6 11.4 Example 10 44 13 3.5 11.5 Example 11 102 13 3.6 10.9 Example 12 195 13 3.6 11.0 Example 13 12 65 3.6 11.3 Example 14 44 65 3.5 11.5 Example 15 78 65 3.5 11.6 Example 16 174 65 3.6 11.0 Comparative HT 1 3.7 8.9 Example 1 Comparative HT 2 3.7 8.6 Example 2 Comparative 12 BD 1 3.8 7.9 Example 3 Comparative 12 BD 2 3.7 7.5 Example 4 Comparative 174 BD 1 3.8 7.7 Example 5 Comparative 174 BD 2 3.7 7.2 Example 6

[0197] As can be seen from [Table 1] above, the organic light-emitting device according to the present invention using the hole transport material (Formula A) in the hole transport layer, and using the dopant material according to the present invention in the light-emitting layer can be operated at a lower voltage and exhibit improved luminous efficacy based on remarkably improved external quantum efficiency compared to the organic light-emitting device using the conventional compound represented by HT, the organic light-emitting device using the conventional compound represented by BD1 and BD2, and the organic light-emitting device without using the combination of materials according to the present invention.

INDUSTRIAL APPLICABILITY

[0198] The organic light-emitting device according to the present invention can be operated at a lower driving voltage and exhibits excellent external quantum efficiency and thus high luminous efficacy by utilizing the compounds having characteristic structures as a hole transport material and a dopant material, respectively, in the hole injection layer or the hole transport layer, and the light-emitting layer, and thus is industrially applicable to flat panel displays, flexible displays, monochromatic or white flat panel lighting systems, monochromatic or white flexible lighting systems, vehicle displays, displays for virtual or augmented reality and the like.