KR100812178B1 - Electroluminescent compounds comprising fluorene group and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to an electroluminescent compound represented by the following Chemical Formula 1 and an electroluminescent device containing the same in the light emitting layer.

[Formula 1]

The electroluminescent compound according to the present invention has an advantage of being able to manufacture an OLED device having good luminous efficiency and excellent life characteristics of a material, and having a very good driving life.

Electroluminescent Compound, Electroluminescent Device, OLED

Description

Electroluminescent compounds containing fluorene group and organic electroluminescent device using the same}

1 is a schematic view showing a cross-sectional structure of an OLED device in Example 1 and Comparative Example 1,

2 is an EL spectrum in Example 1 and Comparative Example 1,

3 is a luminance characteristic curve according to a driving voltage for the OLED of Example 1,

4 is a current density characteristic curve according to a driving voltage for the OLED of Example 1,

5 is a light emission efficiency characteristic curve according to the luminance of the OLED of Example 1.

The present invention relates to a blue light emitting material having high luminous properties and excellent lifespan characteristics and an electroluminescent device containing the same in the light emitting layer.

Among the display elements, an electroluminescence device (EL device) is a self-luminous display element, which has a wide viewing angle, excellent contrast, and fast response speed.Eastman Kodak Co., Ltd. in 1987 An organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer formation material was first developed [Appl. Phys. Lett. 51, 913, 1987].

In organic EL devices, the most important factor that determines the performance of light emission efficiency, lifespan, etc. is a light emitting material. Some of the properties required for such a light emitting material include a high fluorescence quantum yield in a solid state and high mobility of electrons and holes. It should not be easily decomposed during vacuum deposition and should form and stabilize a uniform thin film.

Organic light emitting materials can be classified into high molecular materials and low molecular materials. Low molecular materials include pure organic light emitting materials that do not contain metal complexes and metals in terms of molecular structure. As such light emitting materials, light emitting materials such as chelate complexes such as tris (8-quinolinolato) aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives and oxadiazole derivatives are known. It has been reported that visible light emission from blue to red can be obtained, and the realization of color display elements is expected.

On the other hand, in the case of blue materials, many materials have been developed and commercialized since Idemitsu-Gosan's DPVBi (Formula a), and Idemitsu-Gosan's blue material system and Kodak's dinaphthylanthracen (Formula b), Tetra (t-butyl) perlyene (C) system is known, but much research and development is still required. The system of Idemitsu-high acid disryl compound, which is known to be the most efficient to date, is 6 lm / W for power efficiency and has a device life of more than 30,000 hours. Due to degradation, when applied to a full-color display, the lifetime is only a few thousand hours. Blue light emission is advantageous in terms of luminous efficiency even if the light emission wavelength is shifted toward the longer wavelength, but it is not easy to apply to high-quality display because it does not satisfy pure blue color, and there is a problem in color purity, efficiency and thermal stability, so that research and development It is an urgent part.

[Formula a]

[Formula b]

[Formula c]

Accordingly, an object of the present invention is to provide an electroluminescent compound that compensates for the above-mentioned weaknesses of blue materials and further improves luminous efficiency and device life. The present invention provides an organic EL device having high efficiency and long life.

The present inventors have made an effort to solve the above-mentioned conventional problems, and as a result, have invented a new light emitting compound for realizing an organic EL device having excellent luminous efficiency and a markedly improved lifetime.

Accordingly, the present invention provides a novel blue light emitting material and an electroluminescent device containing the light emitting compound in the light emitting layer. Specifically, the electroluminescent material according to the present invention is characterized in that the compound of Formula 1 below.

[Formula 1]

Ar ₁ is a chemical bond or is selected from the following indenofluorene, fluorene or spiro-fluorene, Ar ₂ is the following indenofluorene, fluorene (fluorene) or spiro-fluorene;

A and B are independently a chemical bond or selected from a phenylene group, a naphthylene group, a biphenylene group, an anthracenylene group, a peryleneylene group or a pyrenylene group, wherein A and Ar ₁ are both chemical bonds Exclude.

R ¹ to R ⁶ are independently C ₁ to C ₂₀ alkyl, cycloalkyl, C ₁ to C ₂₀ alkyl substituted with one or more halogen elements, C ₁ to C ₅ alkyl substituted or unsubstituted phenyl or naph Is selected from til, more preferably R ¹ to R ⁶ are independently selected from C ₁ to C ₅ alkyl, C ₅ to C ₇ cycloalkyl, phenyl or naphthyl, and the halogen element is selected from F, Cl, Selected from Br. R ¹ to R ⁶ may be specifically exemplified by methyl, ethyl, propyl, butyl, amyl, cyclopentyl, cyclohexyl, phenyl, naphthyl and the like.

Ar ₃ to Ar ₆ are independently selected from C ₅ to C ₂₀ aromatic or polycyclic aromatic rings, and may include a hetero element in the aromatic ring.

Ar ₃ to Ar ₆ are independently substituted or unsubstituted with the following alkyl group (R ¹¹ ) phenyl, tolyl, xylyl, pyridyl, biphenyl, naph Naphthyl, anthryl, phenanthryl, pyrenyl, naphthacenyl, acenaphthyl, perylenyl, perylenyl, chrysenyl, fluorine Lantenyl, etc. are preferable, R <^11> is chosen from the C1-C5 alkyl group, n is an integer of 1-5.

The electroluminescent compound of formula 1 according to the present invention may be specifically exemplified by the following compounds.

DIF-1

DSF-1

DPF-1

DMF-1

DIF-2

DSF-2

DPF-2

DMF-2

DIF-3

DSF-3

DPF-3

DMF-3

DTPIF-1

DIF-4

DSF-4

DPF-4

DMF-4

DIF-11

DIF-12

DPF-11

DPF-12

DSF-11

DSF-12

DMF-11

DMF-12

DMF-21

Among the electroluminescent compounds represented by Formula 1 according to the present invention, Ar ₁ and Ar ₂ are the same, Ar ₃ and Ar ₅ are the same, Ar ₄ and Ar ₆ are the same, and A and B are the same, that is, a double bond In the case of symmetry with respect to, it can be prepared by coupling 2 moles of aldehyde compound by MacMurry reaction as shown in Scheme 1.

Scheme 1

In addition, in the case of the asymmetric compound among the compounds of Formula 1, as shown in Scheme 2, the compounds of Formula 4 and Formula 2 prepared from the aldehyde compounds of Formula 3 and halogenated are reacted by Wittig reaction or Wadsworth-Horner-Emmons It can be produced by coupling using a (of Wittig reaction).

Scheme 2

[Ar ₁ to Ar ₆ , A and B in the scheme are as defined above, X represents a halogen element and is Cl or Br.]

Meanwhile, the compound of Chemical Formula 2, which is an important intermediate in preparing the compound according to the present invention, is substituted with dibutyl butyl compound with butyllithium and then reacted with DMF to produce a dibromo aldehyde compound as shown in Scheme 3 below. Secondary amines can then be prepared by substitution in the presence of a catalyst.

Scheme 3

The present invention is not limited only to what is described in the above scheme in preparing the compounds and intermediates according to the present invention, and those skilled in the art can be prepared by applying known organic chemical reactions.

The present invention also provides an electroluminescent device comprising the electroluminescent compound represented by Chemical Formula 1 in a light emitting layer, and more specifically, using an electroluminescent compound of Chemical Formula 1 according to the present invention as a dopant, An electroluminescent element for use in a light emitting layer is provided.

Hereinafter, a novel electroluminescent compound according to the present invention, a method for preparing the same, and a light emitting property of the device will be described with reference to a representative compound of the present invention for a detailed understanding of the present invention. It does not limit the scope of the invention.

Synthesis Example 1 Preparation of DIF- 1 (Compound 120)

Preparation of Compound 112

Compound 111 of 1,4-dibromo - p - xylene (1,4-dibromo-p-xylene ) 200 g (0.76 mol) and phenylboronic acid (phenyl boronic acid) 204 g ( 1.67 mol), Pd ( _{OAc) 2 0.34 g (1.52 mmol} ), and then potassium carbonate, 524 g (3.79 mol), n -Bu 4 NBr 490 g (1.51 mol) was suspended in distilled water to 1.9 L, and the mixture was stirred at 70 ℃ for 24 hours. After completion of the reaction, 2 L of distilled water was added to the reaction solution, and the resulting solid was filtered under reduced pressure to obtain 196 g (0.76 mol) of the compound 112 in the form of a gray solid.

Preparation of Compound 113

After dissolving 196 g (0.76 mol) of compound 112 in 1.23 L (15.17 mol) of pyridine and H ₂ O 2 L, 420 g (2.66 mol) of KMnO ₄ was added to the reaction solution slowly, and the mixture was refluxed for 48 hours.

5 L of distilled water at 50 ° C. was added to remove the by-product solid under reduced pressure, and then 174 g (0.55 mol) of a compound 113 in the form of a white solid formed by adding 3 L of 35% hydrochloric acid was obtained.

Preparation of Compound 114

174 g (0.55 mol) of the obtained compound 113 were added to 1.8 L of concentrated sulfuric acid, and stirred at 25 ° C for 4 hours.

After the reaction was completed, 6 L of ice water was added thereto, stirred for 1 hour, and filtered under reduced pressure to obtain a solid. A solution of 200 g of potassium carbonate dissolved in 5 L of distilled water was added to the solid, stirred for 1 hour, and then filtered under reduced pressure to obtain 120 g (0.43 mol) of a compound 114 as a purple solid.

Preparation of Compound 115

120 g (0.43 mol) of the obtained compound 114 was dissolved in 1.4 L of diethylene glycol, 240 g (4.25 mol) of potassium hydroxide and 207 mL (4.25 mol) of hydrazine hydrate were added thereto at 220 ° C. Stir for 48 hours.

After cooling to room temperature, 4 L of 20% hydrochloric acid solution was added thereto, stirred for 1 hour, and the resulting solid was filtered under reduced pressure to obtain a solid. The solid thus obtained was added with 2 L of acetone and tetrahydrofuran, and stirred for 20 hours, followed by filtration under reduced pressure and drying to give 85 g (0.34 mol, 79% yield) of a compound designated as indenofluorene as a gray solid. )

Preparation of Compound 116

Dissolve compound 115 5.2 g (20.5 mmol) in 50 mL tetrahydrofuran, it was slowly added dropwise n -BuLi (1.6 M in n- Hexane) 29.4 mL (47.0 mmol) at -78 ℃. After reacting for 1 hour, 7.55 mL (53.2 mmol) of iodomethane was added, and then the temperature was gradually raised and stirred at room temperature for 1 hour. Again lowering the temperature of the reaction mixture at -78 ℃ n -BuLi (1.6 M in n-Hexane) 37.1 mL (59.3 mmol) was slowly added to. After 1 hour of reaction, 7.55 mL (53.2 mmol) of iodomethane was added. After slowly raising the temperature and stirring at room temperature for 15 hours, 20 mL of aqueous ammonium chloride solution and 15 mL of distilled water were added to terminate the reaction. The organic layer was removed under reduced pressure, and recrystallized with 100 mL of n-hexane to give 1.7 g (5.48 mmol) of Compound 116. )

Preparation of Compound 117

1.7 g (4.64 mmol) of Compound 116, 11.3 mg (0.07 mmol) of FeCl ₃ were added, and dissolved in 30 mL of chloroform. The temperature was adjusted to 0 ° C. using an ice bath. 0.72 mL (13.9 mmol) of bromine dissolved in 5 mL of chloroform was slowly added dropwise, stirred for 24 hours, and after completion of the reaction, the reaction was terminated with 50 mL of saturated aqueous solution of sodium thiosulfate. After separation, the organic layer was evaporated under reduced pressure, and recrystallized with 100 mL of n -hexane to obtain 1.6 g (3.42 mmol) of compound 117.

Preparation of Compound 118

Dissolve the resulting compound 117 1.6 g (3.42 mmol) in 40 mL tetrahydrofuran, it was slowly added dropwise n -BuLi (1.6 M in n- Hexane) 4.8 mL (3.0mmol) at -78 ℃. After stirring for 30 minutes, 0.3 mL (4.14 mmol) of N, N -dimethyl formamide was added thereto. After slowly raising the temperature and stirring for 2 hours, 20 mL of NH ₄ Cl aqueous solution and 20 mL of distilled water were added to terminate the reaction. The organic layer was separated and removed under reduced pressure, and then methanol: n-hexane (1/1, v / v) 100 Recrystallization from mL afforded 1.1 g (2.64 mmol) of compound 118.

Preparation of Compound 119

1.1 g (2.6 mmol) of the obtained aldehyde compound, 0.67 g (4.0 mmol) of diphenylamine, 1.29 g (3.96 mmol) of cesium carbonate, 18 mg (0.08 mmol) of palladium acetate (Pd (OAc) ₂ ) were added to 100 mL of toluene. After suspension, 32 mg (0.16 mmol) of tri t-butyl phosphine (P ( t -Bu) ₃ ) were added and stirred at 120 ° C. for 4 hours. 30 mL of saturated ammonium chloride aqueous solution was added, extracted with 50 mL of ethyl acetate, filtered, and recrystallized with 50 mL of methanol: n -hexane (1/1, v / v) to obtain 1.2 g (2.4 mmol) of Compound 119.

Preparation of Compound 120

6.0 g (92.4 mmol) of zinc dust, 31 mL (30.8 mmol) of TiCl ₄ , and 26 mL of tetrahydrofuran are stirred at -10 ° C under argon. After 4 hours, 1.2 g (2.4 mmol) of compound 119 were added and stirred for 24 hours. 30 mL of distilled water was added thereto, stirred for 1 hour, and filtered under reduced pressure. Then, 30 mL of acetone and 30 mL of dichloromethane were added thereto, stirred, and filtered under reduced pressure. 50 mL of N, N -dimethylformamide was added to the resulting solid, and the mixture was stirred under reflux for 2 hours, filtered under reduced pressure, and dried to obtain 0.93 g (0.95 mmol, Compound 118) as a yellow solid, yield 72. %) Could be obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 24H), 6.46 (m, 8H), 6.61-6.62 (m, 6H), 6.78 (m, 2H), 6.99-7.01 (m, 10H) , 7.57 (m, 2H), 7.70-7.74 (m, 8H), 7.95 (m, 2H)

MS / FAB: 978 (found) 979.30 (calculated)

Synthesis Example 2 Preparation of DSF- 1 (Compound 125)

Preparation of Compounds 121 and 122

6.27 g (26.9 mmol) of 2-bromobiphenyl and 0.68 g (28.2 mmol) of magnesium powder were added thereto, 5 mL of diethyl ether was added thereto, and the mixture was stirred under reflux for 3 hours. To 10 g (29.6 mmol) of 2,7-Dibromofluorenone (2,7-Dibromofluorenone) was added 5 mL of diethyl ether as a solvent, followed by stirring and slowly added to the reaction mixture solution. After stirring at 25 ° C. for 24 hours, 50 mL of saturated aqueous ammonium chloride solution was placed under an ice bath. The mixture was stirred for 1 hour, filtered, washed with 100 mL of distilled water, and filtered under reduced pressure to obtain crude compound 121, which was then poured into 40 mL of glacial acetic acid and stirred under reflux for 2 hours. 40 mL of 30% hydrochloric acid solution was slowly added to the reaction solution to form a solid, which was filtered under reduced pressure, washed with 100 mL of distilled water, recrystallized with 50 mL of methanol, and dried under reduced pressure to give 9.8 g (20.7 mmol) of Compound 122. Got it.

Preparation of Compound 123

Compound 123 could be obtained by the same method as the synthesis method of compound 118. The compound obtained above, 122 9.8 g (20.7 mmol), in tetrahydrofuran 40 mL, n -BuLi (1.6 M in n-Hexane) 33.6 mL (21 mmol), N, N - dimethylformamide using 2.1 mL (29.0 mmol) The reaction mixture was recrystallized with 30 mL of methanol and 30 mL of n -hexane to obtain 5.23 g (12.36 mmol) of Compound 123.

Preparation of Compound 124

Compound 124 could be obtained by the same method as the synthesis method of compound 119. 5.23 g (12.4 mmol) of aldehyde compound 123 obtained above, 3.14 g (18.5 mmol) of diphenylamine, 6.04 g (18.5 mmol) of cesium carbonate, 83 mg (0.37 mmol) of Pd (OAc) ₂ , 200 mL of toluene, P (t -Bu) _{3 was} reacted with 150 mg (0.74 mmol), and methanol: n -hexane was recrystallized from 100 mL (1/1, v / v) to obtain 3.8 g (7.4 mmol) of Compound 124.

Preparation of Compound 125

Compound 125 could be obtained by the same method as the synthesis method of compound 120. Zinc powder (4.85 g (74.2 mmol), TiCl ₄ (1M solution in dichloromethane) 30 mL (29.7 mmol), tetrahydrofuran 26 mL, using a compound 124 3.8 g (7.4 mmol) of the white powder 2.4 g (2.4 mmol, yield 39%) based on the compound 123 was obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46 (m, 8H), 6.58-6.62 (m, 6H), 7.35 (d, 2H), 6.99-7.01 (m, 10H), 7.16-7.19 (m, 8H), 7.35 (m, 4H), 7.54-7.59 (m, 4H), 7.71-7.72 (m, 6H), 7.84 (d, 2H)

MS / FAB: 990 (found) 991.22 (calculated)

Synthesis Example 3 Preparation of DPF- 1 (Compound 130)

Preparation of Compounds 126 and 127

50 mL of diethyl ether was added to 4.9 g (0.20 mol) of magnesium, and a solution of 31.4 g (0.20 mmol) of bromobenzene in 150 mL of diethyl ether was slowly added dropwise, followed by reflux for 3 hours. Then, a solution of 33.8 g (0.10 mol) of 2,7-dibromofluorenone dissolved in 40 mL of diethyl ether was slowly added dropwise to the reaction mixture and refluxed for 12 hours.

After the reaction was completed, the resulting precipitate was filtered under reduced pressure to obtain 41.5 g (0.10 mmol) of Compound 126. Then, 45 mL of trifluoromethanesulfonic acid was slowly added dropwise while dissolving it in 145 mL of benzene and gradually raising the temperature. . After stirring at 100 ° C. for 30 minutes, the reaction solution was added to ice water to give a solid. The resulting solid was filtered under reduced pressure, washed with 50 mL of methanol and 100 mL of diethyl ether, and then dried under reduced pressure to obtain 27.1 g (57.0 mmol) of the compound 127 as a pale yellow solid.

Preparation of Compound 128

Compound 128 could be obtained by the same method as the synthesis method of compound 118. Using dimethylformamide, 6.2 mL (79.7 mmol), - Compound 127 27.1 g (56.9 mmol), tetrahydrofuran 120 mL, n -BuLi (1.6 M in n-Hexane) 35.6 mL (56.9 mmol), N, N 12.1 g (28.4 mmol) of compound 128 were obtained.

Preparation of Compound 129

Compound 129 was also obtained in the same manner as in the synthesis of Compound 119. Aldehyde compound 128 12.1 g (28.4 mmol), diphenylamine 7.3 g (42.6 mmol), cesium carbonate 13.9 g (42.6 mmol), Pd (OAc) ₂ 192 mg (0.85 mmol), toluene 600 mL, P (t-Bu ) ₃ using 347 mg (1.7 mmol), to give the compound 129 8.8 g (17.1 mmol).

Preparation of Compound 130

Compound 130 could be obtained by the same method as the synthesis method of compound 120. Zinc dust (11.2 g (171 mmol), 69 mL (68.4 mmol) of TiCl ₄ (1 M solution in dichloromethane), 60 mL of tetrahydrofuran and 8.8 g (17.1 mmol) of Compound 124 were used. 5.6 g (5.1 mmol, Compound 35 (yield 35%) based on compound 128) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46 (m, 8H), 6.58-6.62 (m, 6H), 6.75 (d, 2H), 6.99-7.17 (m, 30H), 7.54-7.59 (m, 4H), 7.71 (d, 2H), 7.84 (m, 2H)

MS / FAB: 994 (found) 995.26 (calculated)

Synthesis Example 4 Preparation of DMF- 1 (Compound 134)

Preparation of Compound 131

Under nitrogen, 2,7-dibromofluorene (50.0 g, 154.3 mmol) and 69.2 g (1.23 mol) of potassium hydroxide were dissolved in 700 mL of DMSO, cooled to 0 ° C. and 113 mL of distilled water. Was slowly added dropwise and stirred for 1 hour. Then, 38.5 mL (0.617 mol) of iodine methane (CH ₃ I) was added slowly, and then the temperature was slowly raised and stirred at room temperature for 15 hours. 200 mL of distilled water was added to the reaction solution to terminate the reaction, and extracted with 300 mL of dichloromethane. The resulting organic layer was concentrated under reduced pressure, and then 53.0 g (0.15 mol) of Compound 131 was obtained using silica gel column chromatography (n-hexane: dichloromethane = 20: 1).

Preparation of Compound 132

Compound 132 could be obtained by the same method as the synthesis method of compound 118. Using dimethylformamide, 16.3 mL (211 mmol), - Compound 131 53.0 g (0.15 mol), tetrahydrofuran 350 mL, n -BuLi (1.6 M in n-Hexane) 63.2 mL (158 mmol), N, N 20.9 g (69.4 mmol) of compound 132 were obtained.

Preparation of Compound 133

Compound 133 was obtained by the same method as the synthesis method of compound 119. 20.9 g (69.4 mmol) of aldehyde compound 132, 12.5 g (104.1 mmol) of diphenylamine, 24.1 g (104.1 mmol) of cesium carbonate, 332 mg (2.1 mmol) of Pd (OAc) ₂ , 800 mL of toluene, P (t-Bu ₃ 0.60 g (4.2 mmol) was used to give 15.2 g (39.0 mmol) of Compound 133.

Preparation of Compound 134

Compound 134 could be obtained by the same method as the synthesis method of compound 120. 19.4 g (390 mmol) of zinc dust, 120 mL (156 mmol) of TiCl ₄ (1 M solution in dichloromethane), 104 mL of tetrahydrofuran and 15.2 g (39.0 mmol) of Compound 133 were used. 9.7 g (12.9 mmol, compound 37% yield) of compound 134 (DMF-1) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 12H), 6.46 (m, 8H), 6.58-6.62 (m, 6H), 6.75 (d, 2H), 6.99-7.01 (m, 10H) , 7.54-7.59 (m, 4H), 7.71 (d, 2H), 7.84 (m, 2H)

MS / FAB: 745 (found) 746.98 (calculated)

Synthesis Example 5 Preparation of DIF- 2 (Compound 136)

Preparation of Compound 135

Compound 135 could be obtained by the same method as the synthesis method of compound 119. Aldehyde compound 118 3.0 g (7.2 mmol), N - phenyl-naphthalene-2-amine (N -phenyl naphthalen-2-amine ) 3.5 g (10.8 mmol), cesium carbonate, 1.3 g (10.8 mmol), Pd (OAc) 2 48 2.8 g (5.0 mmol) of Compound 135 were obtained using 87 mg (0.43 mmol) of mg (0.22 mmol), 100 mL of toluene, and P (t-Bu) ₃ .

Preparation of Compound 136

Compound 136 could be obtained by the same method as the synthesis method of compound 120. Zinc powder 4.0 g (60.4 mmol), TiCl ₄ (1 M in dichloromethane) 21 mL (20.1 mmol), 50 mL tetrahydrofuran and compound 135 2.8 g (5.0 mmol) to give a yellow solid 2.3 g (2.1 mmol, yield 58%) of 136 (DIF-2) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 24H), 6.46 (m, 4H), 6.61-6.62 (m, 4H), 6.76-6.78 (m, 6H), 6.99-7.09 (m, 8H), 7.23 (m, 2H), 7.44-7.55 (m, 8H), 7.70-7.74 (m, 8H), 7.95 (m, 2H)

MS / FAB: 1078 (found) 1079.41 (calculated)

Synthesis Example 6 Preparation of DSF- 2 (Compound 138)

Preparation of Compound 137

Compound 137 could be obtained by the same method as the synthesis method of compound 119. Aldehyde compound 123 6.8 g (16.0 mmol), N - phenyl-naphthalene-2-amine (N -phenyl naphthalen-2-amine ) 5.3 g (24.0 mmol), cesium carbonate, 7.8 g (24.1 mmol), Pd (OAc) 2 107 7.5 g (13.3 mmol) of Compound 137 was obtained using 194 mg (0.96 mmol) of mg (0.48 mmol), 150 mL of toluene, and P (t-Bu) ₃ .

Preparation of Compound 138

Compound 138 was obtained by the same method as the synthesis method of compound 120. Zinc dust (8.7 g (133 mmol), 53 mL (53.2 mmol) of TiCl ₄ (1 M solution in dichloromethane), 65 mL of tetrahydrofuran and 7.5 g (13.3 mmol) of compound 137 were obtained as a light gray solid. 8.1 g (7.5 mmol, 93% yield) of compound 138 (DSF-2) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46 (m, 4H), 6.58-6.62 (m, 4H), 6.75-6.79 (m, 6H), 6.99-7.23 (m, 18H), 7.71 (m, 4H), 7.44-7.59 (m, 10H), 7.71-7.72 (m, 6H), 7.84 (m, 2H)

MS / FAB: 1090 (found) 1091.34 (calculated)

Synthesis Example 7 Preparation of DPF- 2 (Compound 140)

Preparation of Compound 139

Compound 139 could be obtained by the same method as the synthesis method of compound 119. Aldehyde compound 128 6.8 g (16.0 mmol), N - phenyl-naphthalene-2-amine (N -phenyl naphthalen-2-amine ) 5.3 g (24.0 mmol), cesium carbonate, 7.8 g (24.1 mmol), Pd (OAc) 2 107 7.5 g (13.3 mmol) of compound 139 was obtained using 194 mg (0.96 mmol) of mg (0.48 mmol), 150 mL of toluene, and P (t-Bu) ₃ .

Preparation of Compound 140

Compound 140 could be obtained by the same method as the synthesis method of compound 120. Zinc dust (8.7 g (133 mmol), TiCl ₄ (1 M solution in dichloromethane) 53 mL (53.2 mmol), 65 mL tetrahydrofuran, compound 139 7.48 g (13.3 mmol), a light gray solid 8.1 g (7.5 mmol, 93% yield) of compound 140 (DPF-2) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46 (m, 4H), 6.58-6.62 (m, 4H), 6.75-6.79 (m, 6H), 6.99-7.23 (m, 30H), 7.44-7.59 ( m, 10H), 7.06 (m, 2H), 7.84 (m, 2H)

MS / FAB: 1096 (found) 1095.37 (calculated)

Synthesis Example 8 Preparation of DMF- 2 (Compound 142)

Preparation of Compound 141

Compound 141 was obtained by the same method as the synthesis method of compound 119. Aldehyde compound 132 5.3 g (17.5 mmol), N - phenyl-naphthalene-2-amine (N -phenyl naphthalen-2-amine ) 4.1 g (26.3 mmol), cesium carbonate, 6.1 g (26.3 mmol), Pd (OAc) 2 84 5.8 g (13.2 mmol) of Compound 141 were obtained using 152 mg (1.1 mmol) of mg (0.52 mmol), 117 mL of toluene, and P (t-Bu) ₃ .

Preparation of Compound 142

Compound 142 was obtained by the same method as the synthesis method of compound 120. Zinc dust 6.7 g (68.0 mmol), TiCl ₄ (1 M solution in dichloromethane) 41 mL (27.2 mmol), 50 mL tetrahydrofuran, compound 139 5.8 g (6.8 mmol) were used as light gray solid. 6.3 g (7.4 mmol, yield 84%) of compound 142 (DMF-2) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 12H), 6.46-6.62 (m, 8H), 6.76-6.79 (m, 6H), 6.99-7.09 (m, 8H), 7.23 (m, 2H), 7.44-7.59 (m, 10H), 7.71 (m, 2H), 7.84 (m, 2H)

MS / FAB: 846 (found) 847.10 (calculated)

Synthesis Example 9 Preparation of DIF- 3 (Compound 144)

Preparation of Compound 143

Compound 143 could be obtained by the same method as the synthesis method of compound 119. 5.0 g (12.0 mmol) of aldehyde compound 118, 4.8 g (18.0 mmol) of di (naphthalen-3-yl) amine, 5.9 g (18.0 mmol) of cesium carbonate, Pd (OAc) ₂ 81 mg (0.36 mmol), 90 mL of toluene, and 145 mg (0.72 mmol) of P (t-Bu) ₃ were obtained to obtain 5.7 g (9.5 mmol) of Compound 143.

Preparation of Compound 144

Compound 144 could be obtained by the same method as the synthesis method of compound 120. Zinc dust 7.4 g (0.11 mol), TiCl ₄ (1 M in dichloromethane) 38 mL (38 mmol), tetrahydrofuran 75 mL and compound 143 using 5.7 g (9.5 mmol) is a yellow solid 4.0 g (3.4 mmol, yield 57%) were obtained for 144 (DIF-3).

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 24H), 6.61-6.79 (m, 12H), 6.99 (d, 2H), 7.09-7.23 (m, 8H), 7.44-7.57 (m, 14H), 7.70-7.74 (m, 8H), 7.95 (m, 2H)

MS / FAB: 1178 (found) 1179.53 (calculated)

Synthesis Example 10 Preparation of DSF- 3 (Compound 146)

Preparation of Compound 145

Compound 145 could be obtained by the same method as the synthesis method of compound 119. 5.9 g (13.9 mmol) of aldehyde compound in spiro form, 4.8 g (18.0 mmol) of di (naphthalen-3-yl) amine, 6.8 g (20.9 mmol) of cesium carbonate, Pd 6.6 g (10.7 mmol) of Compound 145 was obtained using 93 mg (0.42 mmol) of (OAc) ₂ , 90 mL of toluene, and 169 mg (0.84 mmol) of P (t-Bu) ₃ .

Preparation of Compound 146

Compound 146 could be obtained by the same method as the synthesis method of compound 120. 7.0 g (0.11 mol) of zinc dust, 43 mL (43 mmol) of TiCl ₄ (1 M solution in dichloromethane), 65 mL of tetrahydrofuran and 6.6 g (10.7 mmol) of Compound 145 were used as a gray solid. 7.0 g (5.9 mmol, yield 84%) of compound 146 (DSF-3) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.58 (m, 2H), 6.75-6.79 (m, 10H), 6.99 (s, 2H), 7.09-7.23 (m, 16H), 7.35-7.55 (m, 20H), 7.71-7.72 (m, 6H), 7.84 (m, 2H)

MS / FAB: 1190 (found) 1191.46 (calculated)

Synthesis Example 11 Preparation of DPF- 3 (Compound 148)

Preparation of Compound 147

Compound 147 could be obtained by the same method as the synthesis method of compound 119. 4.3 g (10.1 mmol) of aldehyde compounds in spiro form, 3.5 g (15.2 mmol) of di (naphthalen-3-yl) amine, 5.0 g (15.2 mmol) of cesium carbonate, Pd 4.8 g (7.8 mmol) of Compound 147 was obtained using 68 mg (0.30 mmol) of (OAc) ₂ , 66 mL of toluene, and 123 mg (0.61 mmol) of P (t-Bu) ₃ .

Preparation of Compound 148

Compound 148 was obtained by the same method as the synthesis method of compound 120. Zinc dust 5.1 g (78.0 mmol), TiCl ₄ (1 M solution in dichloromethane) 31 mL (31.2 mmol), 47 mL tetrahydrofuran, 147 g 4.8 g (7.8 mmol) were used as a gray solid. 5.1 g (4.2 mmol, yield 83%) of compound 148 (DPF-3) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.58 (m, 2H), 6.75-6.79 (m, 10H), 6.99-7.23 (m, 30H), 7.44-7.55 (m, 16H), 7.71-7.84 ( m, 4H)

MS / FAB: 1194 (found) 1195.49 (calculated)

Synthesis Example 12 Preparation of DMF- 3 (Compound 150)

Preparation of Compound 149

Compound 149 could be obtained by the same method as the synthesis method of compound 119. 5.6 g (18.5 mmol) of aldehyde compound in spiro form, 4.6 g (27.8 mmol) of di (naphthalen-3-yl) amine, 6.5 g (27.8 mmol) of cesium carbonate, Pd 6.3 g (12.8 mmol) of Compound 149 was obtained using 89 mg (0.56 mmol) of (OAc) ₂ , 86 mL of toluene, and 160 mg (1.11 mmol) of P (t-Bu) ₃ .

Preparation of Compound 144

Compound 150 could be obtained by the same method as the synthesis method of compound 120. Zinc solid 6.7 g (0.128 mol), TiCl ₄ (1 M solution in dichloromethane) 41 mL (51.2 mmol), 62 mL tetrahydrofuran and 149 g (12.8 mmol) compound 149 7.5 g (7.9 mmol, yield 85%) of compound 150 (DMF-3) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 12H), 6.58 (m, 2H), 6.75-6.79 (m, 10H), 6.99 (s, 2H), 7.09-7.23 (m, 8H) , 7.44-7.55 (m, 16H), 7.71 (m, 2H), 7.84 (m, 2H)

MS / FAB: 946 (found) 947.21 (calculated)

Synthesis Example 13 Preparation of DTPIF- 1 (Compound 155)

Preparation of Compound 151

59 mL of diethyl ether was added to 5.8 g (0.283 mol) of magnesium, and 37.2 g (0.283 mol) of bromobenzene diluted in 178 mL of diethyl ether was slowly added dropwise. The reaction solution was stirred under reflux for 3 hours, and then a solution of 20.0 g (70.8 mmol) of Compound 114 in 47 mL of diethyl ether was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at reflux for 12 hours. After completion of the reaction, the formed precipitate was filtered under reduced pressure to give 24.6 g (44.0 mmol) of an intermediate product, which was dissolved in 172 mL of benzene and slowly added dropwise to 53 mL of trifluoromethanesulfonic acid while gradually raising the temperature. After stirring at 100 ° C. for 30 minutes, the reaction solution was added to 200 mL of ice water, and the resulting solid was filtered under reduced pressure, washed with 59 mL of methanol and 119 mL of diethyl ether, and dried under reduced pressure to obtain 32.1 g (57.4) as a light yellow solid. mmol).

Preparation of Compound 152

Add 32.1 g (57.4 mmol) of compound 151 and 56 mg of iron (III) chloride, dissolve in 338 mL of chloroform, add 33.9 g (121 mmol) of bromine diluted with 56 mL of chloroform to a dropping funnel, It was slowly added dropwise at 0 ℃. After completion of the dropwise addition, the mixture was stirred for 1 hour, the reaction was terminated with a saturated aqueous solution of sodium thiosulfate, extracted with 500 mL of dichloromethane, the organic layer was dried and filtered, and dichloromethane: hexane (1/1, v / v). ) Recrystallized from 200 mL to give 33.0 g (46.0 mmol) of Compound 152.

Preparation of Compound 153

Compound 153 could be obtained by the same method as the synthesis method of compound 118. Using dimethylformamide, 6.2 mL (64.4 mmol), - Compound 152 33.0 g (46.0 mmol), tetrahydrofuran 146 mL, n -BuLi (1.6 M in n-Hexane) 43 mL (55.2 mmol), N, N 23.0 g (34.5 mmol) of compound 153 were obtained.

Preparation of Compound 154

Compound 154 could be obtained by the same method as the synthesis method of compound 119. Aldehyde compound 153 23.0 g (34.5 mmol), diphenylamine 13.8 g (51.8 mmol), cesium carbonate 26.4 g (51.8 mmol), Pd (OAc) ₂ 365 mg (1.0 mmol), toluene 1,2 L, P (t -Bu) ₃ 660 mg (2.1 mmol) gave 23.4 g (31.0 mmol) of compound 154.

Preparation of Compound 155

Compound 155 could be obtained by the same method as the synthesis method of compound 120. Zinc powder 30.0 g (0.31 mol), TiCl ₄ (1 M solution in dichloromethane) 183 mL (0.124 mol), 160 mL tetrahydrofuran and Compound 154 23.4 g (31.0 mmol) 14.9 g (10.0 mmol, compound 57% yield) of Compound 155 (DTPIF-1) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46 (m, 8H), 6.61-6.62 (m, 6H), 6.78 (m, 2H), 7.01-7.14 (m, 50H), 7.57 (m, 2H) , 7.67-7.70 (m, 8H), 7.95 (m, 2H)

MS / FAB: 1474 (found) 1475.85 (calculated)

Synthesis Example 14 Preparation of DIF- 4 (Compound 157)

Preparation of Compound 156

Compound 156 was obtained by the same method as the synthesis method of compound 119. Aldehyde compound 118 10.0 g (24.0 mmol), N - phenyl-biphenyl amine (N -phenylbiphenylamine) 8.8 g (36.0 mmol), cesium carbonate 11.7 g (36.0 mmol), Pd (OAc) 2 161 mg (0.72 mmol) toluene 90 mL, P ( t- Bu) ₃ 291 mg (1.44 mmol) gave 12.6 g (21.6 mmol) of compound 156.

Preparation of Compound 157

Compound 157 was obtained by the same method as the synthesis method of compound 120. Zinc powder 17.0 g (0.26 mol), TiCl ₄ (1 M in dichloromethane) 86 mL (86 mmol), tetrahydrofuran 150 mL and compound 156 using 12.6 g (21.6 mmol) as a yellow solid 5.6 g (5.0 mmol, yield 41%) of 157 (DIF-4) was obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 24H), 6.46-6.62 (m, 12H), 6.78 (m, 2H), 6.99-7.01 (m, 6H), 7.22-7.32 (m, 10H), 7.48-7.57 (m, 6H), 7.70-7.73 (m, 8H), 7.95 (m, 2H)

MS / FAB: 1130 (found) 1131.49 (calculated)

Synthesis Example 15 Preparation of DSF- 4 (Compound 159)

Preparation of Compound 158

Compound 158 was obtained by the same method as the synthesis method of compound 119. Spiro form of an aldehyde compound 123 4.54 g (10.7 mmol), N - phenyl-biphenyl amine (N -phenylbiphenylamine) 4.4 g (18.0 mmol), cesium carbonate 5.25 g (16.1 mmol), Pd (OAc) 2 71.6 mg (0.32 mmol ), 4.16 g (7.1 mmol) of compound 158 was obtained using 75 mL of toluene, 130 mg (0.65 mmol) of P ( t- Bu) ₃ .

Preparation of Compound 159

Compound 159 could be obtained by the same method as the synthesis method of compound 120. Using zinc dust 4.7 g (70.8 mmol), TiCl ₄ (1 M solution in dichloromethane) 29 mL (28.3 mmol), 40 mL tetrahydrofuran and 4.158 g (7.1 mmol) compound 158, 6.02 g (5.2 mmol, 97% yield) of compound 159 (DSF-4) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46-6.58 (m, 12H), 6.75 (d, 2H), 6.99-7.01 (m, 6H), 7.16-7.32 (m, 22H), 7.48-7.59 ( m, 8H), 7.71-7.84 (m, 8H)

MS / FAB: 1142 (found) 1143.42 (calculated)

Synthesis Example 16 Preparation of DPF- 4 (Compound 161)

Preparation of Compound 160

Compound 160 could be obtained by the same method as the synthesis method of compound 119. Spiro (spiro-) in the form of an aldehyde compound 128 4.0 g (9.40 mmol), N - phenyl-biphenyl amine (N -phenylbiphenylamine) 3.9 g (14.1 mmol), cesium carbonate, 4.6 g (14.1 mmol), Pd (OAc) 2 3.7 g (6.2 mmol) of Compound 160 was obtained using 63 mg (0.28 mmol), 66 mL of toluene, and 115 mg (0.56 mmol) of P ( t- Bu) ₃ .

Preparation of Compound 161

Compound 161 could be obtained by the same method as the synthesis method of compound 120. Zinc dust 4.2 g (62.0 mmol), TiCl ₄ (1 M solution in dichloromethane) 26 mL (24.8 mmol), 36 mL tetrahydrofuran, compound 160 3.7 g (6.2 mmol) 5.3 g (4.6 mmol, 98% yield) of 161 (DPF-4) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46-6.62 (m, 12H), 6.75 (d, 2H), 6.99-7.32 (m, 36H), 7.48-7.59 (m, 8H), 7.71 (m, 2H), 7.84 (m, 2H)

MS / FAB: 1176 (found) 1147.75 (calculated)

Synthesis Example 17 Preparation of DMF- 4 (Compound 163)

Preparation of Compound 162

Compound 162 is an aldehyde compound 132 6.0 g (19.9 mmol) in the same manner as in the synthesis method of Compound 119, N - phenyl-biphenyl amine (N -phenylbiphenylamine) 5.8 g (29.9 mmol), cesium carbonate, 6.9 g (29.9 mmol), Pd 5.5 g (11.8 mmol) of Compound 162 were obtained by recrystallization from 60 mL of methanol using (OAc) ₂ 65 mg (0.60 mmol), 99 mL of toluene, 172 mg (1.2 mmol) of P ( t- Bu) ₃ .

Preparation of Compound 163

Compound 163 could be obtained by the same method as the synthesis method of compound 120. Using 6.2 g (118.0 mmol) of zinc dust, 38 mL (47.2 mmol) of TiCl ₄ (1 M solution in dichloromethane), 53 mL of tetrahydrofuran and 5.5 g (11.8 mmol) of Compound 162, 8.0 g (8.8 mmol, yield 88%) of compound 163 (DMF-4) were obtained.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 12H), 6.46-6.62 (m, 12H), 6.75 (m, 2H), 6.99-7.01 (m, 6H), 7.22-7.32 (m, 10H), 7.48-7.59 (m, 8H), 7.71-7.84 (m, 4H)

MS / FAB: 888 (found) 899.17 (calculated)

Synthesis Example 18 Preparation of DIF-11 (Compound 169)

Preparation of Compound 164

1.2 g (2.4 mmol) of Compound 119 and 0.1 g (3.6 mmol) of NaBH ₄ were dissolved in 20 mL of tetrahydrofuran, cooled to 0 ° C., and 10 mL of methanol was slowly added dropwise. After stirring for 30 minutes, 50 mL of distilled water was added to terminate the reaction. The mixture was extracted with 30 mL of ethyl acetate, and dried under reduced pressure to obtain 0.9 g (1.8 mmol) of Compound 164 by column chromatography (dichloromethane / hexane = 1/1).

Preparation of Compound 165

0.9 g (1.8 mmol) of Compound 164 is added to a reaction vessel, and 20 mL of triethyl phosphite is dissolved under a stream of nitrogen. Add 10 mL of triethylphosphite to another reactor and open the lid 0.6 g (1.8 mmol) was added little by little and stirred at 0 ° C. for 30 minutes. This mixture with iodine and triethylphosphite is placed in a reaction vessel containing compound 109. The temperature was raised to 150 ℃ and stirred for 4 hours. After the reaction was completed, triethyl phosphite was removed by distillation under reduced pressure, washed with 500 mL of water, extracted with 500 mL of ethyl acetate, and dried under reduced pressure. Compound 165 1.1 g (ethyl acetate / hexane = 1/1) was purified by column chromatography. 1.7 mmol).

Preparation of Compound 166

Triphenylamine (Triphenylamine) 5.0 g (20.4 mmol ), N - bromo mossuk siniyi imide (N -bromo-succinimide) was stirred for 3.6 g (20.4 mmol) in 25 ℃ then dissolved in 40 mL of dichloromethane in a nitrogen atmosphere for 5 hours It was. Then, 100 mL of distilled water was added to terminate the reaction. Then, the mixture was extracted with 30 mL of dichloromethane, dried under reduced pressure, and recrystallized from 100 mL of hexane to obtain 5.2 g (16.0 mmol) of the target compound.

Preparation of Compound 167

5.2 g (16.0 mmol) of the obtained compound 166 were dissolved in 100 mL of purified tetrahydrofuran under a stream of nitrogen, and then cooled to -78 ° C, where 15.0 mL (24.0 mmol) of n -butyllithium (1.6M in Hexane) was slowly added. After dropping, the mixture was stirred for 1 hour. And 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ) 6.5 mL (32.0 mmol) was added. After slowly raising the temperature and stirring the mixture at 25 ° C. for one day, 200 mL of distilled water was added to terminate the reaction. The mixture was extracted with 100 mL of ethyl acetate, dried under reduced pressure, and recrystallized from 20 mL of tetrahydrofuran and 200 mL of methanol. (8.6 mmol) was obtained.

Preparation of Compound 168

The temperature was set at 120 ° C. in advance, and then 5.0 g (11.9 mmol) of Compound 118, 5.3 g (14.4 mmol) of Compound 167, 1.4 g (1.2 mmol) of tetrakis palladium triphenylphosphine (Pd (PPh ₃ ) ₄ ), 0.6 mL (1.2 mmol) of aliquat336 was dissolved in 100 mL of toluene, and then 60 mL of 2M aqueous potassium carbonate solution was added thereto, and the mixture was stirred under reflux for 4 hours. Then, the temperature was lowered to 25 ° C., 150 mL of distilled water was added to terminate the reaction, extracted with 100 mL of ethyl acetate, dried under reduced pressure, and recrystallized with 100 mL of methanol and 20 mL of tetrahydrofuran to obtain 5.8 g (9.9 mmol) of the title compound. .

Preparation of Compound 169

6.2 g (9.9 mmol) of the compound 165 and 5.8 g (9.9 mmol) of the compound 168 were added to a reaction vessel, followed by drying under reduced pressure. After making nitrogen atmosphere, 200 mL of tetrahydrofuran was added and dissolved. Then, the mixture was cooled to 0 ° C, and 1.7 g (14.8 mmol) of potassium tert-butoxide (t-BuOK) was dissolved in 20 mL of tetrahydrofuran and slowly added dropwise thereto. . After stirring for 2 hours at 0 ℃, 300 mL of distilled water was added and stirred. At this time, a solid was produced, which was filtered under reduced pressure to obtain a solid. Wash with 200 mL of methanol and repeat three times. Washed with 50 mL of ethyl acetate and recrystallized with 50 mL of tetrahydrofuran and 300 mL of methanol to obtain 5.7 g (5.4 mmol, 55%) of the title compound.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.68 (s, 24H), 6.46-6.62 (m, 15H), 6.75 (m, 1H), 6.99-7.01 (m, 10H), 7.24 (m, 2H) , 7.54-7.69 (m, 6H), 7.71-7.77 (m, 4H), 8.06-8.12 (m, 12H),

MS / FAB: 1054 (found) 1055.4 (calculated)

Synthesis Example 19 Preparation of DIF-12 (Compound 170)

A compound 302 2.8 g (2.5 mmol, 48%) was obtained in the same manner as the compound 120 preparation method of Synthesis Example 1, except that Compound 168 3.0g (5.1 mmol) was used instead of Compound 119.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 24H), 6.45-6.52 (m, 12H), 6.64 (m, 4H), 6.99-7.02 (m, 10H), 7.23 (m, 4H) , 7.57-7.63 (m, 4H), 7.73-7.74 (m, 6H), 7.80 (m, 2H), 7.95-8.01 (m, 4H)

MS / FAB: 1130 (found) 1131.4 (calculated)

Synthesis Example 20 Synthesis of DPF-11 (Compound 174)

Preparation of Compound 172

8.8 g (17.1 mmol) of the compound 129 prepared in Synthesis Example 3 was used to obtain the desired compound 172 7.6 g (11.9 mmol) in the same manner as in Synthesis Example 18.

Preparation of Compound 174

Compound 173 was prepared in the same manner as in Synthesis Example 18 from 12.1 g (28.4 mmol) of Compound 128 prepared in Synthesis Example 3, and then reacted with Compound 172 to obtain 4.2 g (3.9 mmol) of the target compound 174.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46-6.52 (m, 12H), 6.75 (m, 1H), 6.99-7.17 (m, 32H), 7.54-7.60 (m, 4H), 7.71 (m, 2H), 7.77 (m, 1 H), 7.84-7.92 (m, 3 H)

MS / FAB: 1070 (found) 1071.3 (calculated)

Synthesis Example 21 Preparation of DPF-12 (Compound 175)

Except for using Compound 173 3.0g (5.1 mmol) instead of Compound 119 was carried out in the same manner as the Preparation of Compound 120 of Synthesis Example 1 to obtain 2.5 g (2.2 mmol, 43%) of the compound 175 as a yellow solid.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46-6.52 (m, 12H), 6.62 (m, 4H), 6.99-7.23 (m, 34H), 7.54-7.60 (m, 4H), 7.71-7.77 ( m, 4H), 7.84-7.90 (m, 4H)

MS / FAB: 1130 (found) 1131.4 (calculated)

Synthesis Example 22 Preparation of DSF-11 (Compound 179)

Preparation of Compound 177

4.3 g (8.4 mmol) of the compound 124 prepared in Synthesis Example 2 were used to obtain 3.6 g (5.7 mmol) of the desired compound 177.

Preparation of Compound 179

Compound 178 was prepared by the same method as Synthesis Example 18 from 5.0 g (11.8 mmol) of the compound 123 prepared in Synthesis Example 2, and then reacted with compound 177, to obtain 3.8 g (3.6 mmol) of the target compound 305.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46-6.62 (m, 15H), 6.75 (m, 1H), 6.93-7.01 (m, 10H), 7.16-7.23 (m, 10H), 7.35 (m, 4H), 7.54-7.60 (m, 4H), 7.71-7.90 (m, 10H)

MS / FAB: 1066 (found) 1067.3 (calculated)

Synthesis Example 23 Preparation of DSF-12 (Compound 180)

3.5 g (3.3 mmol, 60%) of Compound 180 was obtained in the same manner as the compound 120 preparation method of Synthesis Example 1, except that 3.0 g (5.1 mmol) of Compound 178 was used instead of Compound 119.

¹ H NMR (CDCl ₃ , 200 MHz): δ 6.46-6.52 (m, 12H), 6.62 (m, 4H), 6.99-7.02 (m, 10H), 7.16-7.23 (m, 12H), 7.35 (m, 4H), 7.54-7.60 (m, 4H), 7.71-7.72 (m, 8H), 7.84-7.91 (m, 4H)

MS / FAB: 1142 (found) 1143.4 (calculated)

Synthesis Example 24 Preparation of DMF-11 (Compound 184)

Preparation of Compound 182

5.0 g (12.8 mmol) of the compound 133 prepared in Synthesis Example 4 were used to obtain 4.4 g (8.6 mmol) of the desired compound 182.

Preparation of Compound 184

Compound 183 was prepared in the same manner as in Synthesis Example 18 from 5.0 g (16.6 mmol) of the compound 132 prepared in Synthesis Example 4, and then reacted with Compound 182 to obtain 3.8 g (3.6 mmol) of the target compound 184.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 12H), 6.46-6.62 (m, 15H), 6.75 (d, 1H), 6.99-7.01 (m, 10H), 7.23 (m, 2H) , 7.54-7.59 (m, 4H), 7.71 (m, 2H), 7.77-7.90 (m, 4H)

MS / FAB: 822 (found) 823.1 (calculated)

Synthesis Example 25 Preparation of DMF-12 (Compound 185)

Except for using Compound 183 3.0 g (6.4 mmol) instead of Compound 119 and proceeding in the same manner as in the Preparation of Compound 120 of Synthesis Example 1 3.4 g (3.8 mmol, 60%) of the compound 185 as a yellow solid.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 12H), 6.46-6.52 (m, 12H), 6.62 (m, 4H), 6.99-7.01 (m, 10H), 7.23 (m, 4H) , 7.54-7.60 (m, 4H), 7.71-7.90 (m, 8H)

MS / FAB: 898 (found) 899.1 (calculated)

Synthesis Example 26 Preparation of DMF-21 (Compound 187)

Preparation of Compound 186

A triphenylamine 10.0 g (40.7 mmol) N, N-dimethylformamide was dissolved in 100 mL and then cooled to 0 ℃, N, N the other vessel placed in dimethylformamide 32 mL (407.6 mmol) was cooled to 0 ℃ POCl _{3 was} then slowly added. After stirring for 30 minutes, the mixture was slowly added dropwise at 0 ° C. to a container in which triphenylamine was dissolved. The mixture was further stirred at 45 ° C. for 18 hours, followed by slowly pouring a saturated aqueous sodium hydroxide solution and stirring with excess water. At this time, a solid was formed, which was filtered, washed twice with water and twice with methanol to obtain 10.0 g (36.6 mmol) of the target compound 186.

Preparation of Compound 187

2.1 g (7.8 mmol) of the compound 186 was reacted with the compound 182 in the same manner as in Synthesis example 18 to obtain 3.0 g (4.7 mmol, 62%) of the title compound 187.

¹ H NMR (CDCl ₃ , 200 MHz): δ 1.67 (s, 6H), 6.46 (m, 10H), 6.58-6.62 (m, 5H), 6.75 (m, 1H), 6.79-7.01 (m, 10H) , 7.17 (m, 2H), 7.54-7.59 (m, 2H), 7.71 (m, 1H), 7.84 (m, 1H)

MS / FAB: 629 (found) 630.8 (calculated)

Example 1 Fabrication of OLED Device

Using the light emitting material of the present invention as a dopant, an OLED device was fabricated as shown in FIG.

First, the transparent electrode ITO thin film (15 Ω / □) (2) obtained from the glass for OLED (1) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water sequentially, and then placed in isopropanol. It was used after.

Next, an ITO substrate is installed in the substrate folder of the vacuum deposition apparatus, and 2-TNATA (4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino having the following structure in a cell in the vacuum deposition apparatus). ) triphenylamine) and evacuated until the vacuum in the chamber reaches 10-6 torr. Then, a current is applied to the cell to evaporate 2-TNATA to form a hole injection layer 3 having a thickness of 60 nm on the ITO substrate. Deposited.

Subsequently, NPB (N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine) was added to another cell in the vacuum deposition apparatus, and NPB By evaporation, a hole transport layer 4 having a thickness of 20 nm was deposited on the hole injection layer.

After the hole transport layer was formed, the light emitting layer 5 was deposited thereon as follows. DNA (dinaphthylanthracene) having the following structure as a light emitting material in one cell in the vacuum deposition equipment, and a light emitting material of a compound (for example, compound DPF-1) according to the present invention in each cell, the deposition rate is 100: A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer.

Subsequently, Alq (tris (8-hydroxyquinoline) -aluminum (III)) having the following structure was deposited with the electron transport layer 6 to a thickness of 20 nm, and then the compound Liq (lithium quinolate) having the following structure was used as the electron injection layer 7. ) Was deposited to a thickness of 1 to 2 nm, and then an Al cathode 8 was deposited to a thickness of 150 nm using another vacuum deposition equipment to fabricate an OLED.

Each material used in the OLED device was vacuum sublimated and purified under 10 ^-6 torr, respectively, to be used for device fabrication.

Comparative Example 1 OLED device fabrication using conventional light emitting material

After the hole injection layer 3 and the hole transport layer 4 were formed in the same manner as in Example 1, one cell of the vacuum deposition equipment was placed with dinaphthylanthracene (DNA), a blue light emitting material, and the other. After putting perylene having the following structure, which is another blue light emitting material, into the cell, a light emitting layer 5 having a thickness of 30 nm was deposited on the hole transport layer at a deposition rate of 100: 1.

Subsequently, the electron transport layer 6 and the electron injection layer 7 were deposited in the same manner as in Example 1, and the Al cathode 8 was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED. .

Example 2 Luminescence Characteristics of the Fabricated OLED Device

The luminous efficiency of the organic light emitting compound according to the present invention prepared in Example 1 and Comparative Example 1 and the conventional light emitting compound containing OLED is measured at 500 cd / m 2 and 2,000 cd / m 2, respectively, and are shown in Table 1 below. . Particularly, in the case of the blue light emitting material, the light emission characteristics in the low luminance region and the luminance applied to the panel are very important, and thus the luminance data is about 2,000 cd / m 2 to reflect this.

TABLE 1

As shown in Table 1, based on the "luminescence efficiency / Y" value showing a similar tendency to the quantum efficiency, a comparative example which is an OLED device containing DNA: perylene which is a well-known conventional light emitting material according to the present invention and Comparing OLED devices using organic light emitting compounds as light emitting materials, OLED devices using organic light emitting compounds according to the present invention as light emitting materials showed higher "luminescence efficiency / Y" values.

As the organic light emitting compound according to the present invention exhibits a high "luminescence efficiency / Y" value, it was found that the organic light emitting compounds of the present invention are a material having a high quantum efficiency. It can be seen that it can realize high efficiency while having the color coordinate equivalent to that of the compound. In particular, in the case of the DPF-1, 2, 3 series, it was confirmed that the "luminescence efficiency / Y" value is improved by 2.5 to 3 times compared with the conventional light emitting material.

Therefore, the organic light emitting compound of the present invention can be used as a high efficiency blue light emitting material, and has great advantages in terms of brightness, power consumption, and lifespan of a conventional full color OLED.

2 shows EL spectra of DPF-1, which is a light emitting material of the present invention, and Comparative Example 1, and FIGS. 3 to 5 show current density-voltage characteristics of an OLED containing a DPF-1 device, which is a light emitting material of the present invention; The luminance-voltage characteristics of the OLED and the luminous efficiency-current density characteristics of the OLED are shown. 3 to 5, the current density-voltage characteristics of the OLED, the luminance-voltage characteristics of the OLED, and the luminous efficiency-current density characteristics of the OLED were very excellent.

The new electroluminescent compound according to the present invention is used in the light emitting layer of the electroluminescent device, and has an advantage of producing an OLED device having a good luminous efficiency and excellent life characteristics of the material and having a very good driving life.

Claims (6)

An electroluminescent compound represented by the following formula (1). [Formula 1]

Ar ₁ is a chemical bond or is selected from the following indenofluorene, fluorene or spiro-fluorene, Ar ₂ is the following indenofluorene, fluorene (fluorene) or spiro-fluorene;

A and B are independently a chemical bond or are selected from phenylene group, naphthylene group, biphenylene group, anthracenylene group, peryleneylene group or pyrenylene group; R ¹ to R ⁶ are independently C ₁ to C ₂₀ alkyl, cycloalkyl, C ₁ to C ₂₀ alkyl substituted with one or more halogen elements, C ₁ to C ₅ alkyl substituted or unsubstituted phenyl or naph Selected from til; Ar ₃ to Ar ₆ are independently selected from C ₅ to C ₂₀ aromatic or polycyclic aromatic rings, and may include a hetero element in the aromatic ring; In the formula, except that A and Ar ₁ are both chemical bonds. The method of claim 1, Ar ₃ to Ar ₆ are independently selected from the following structures;

R ¹¹ is selected from a C ₁ to C ₅ alkyl group which is optionally substituted with a halogen element; n is an integer of 1 to 5, characterized in that the electroluminescent compound. The method of claim 2, R ¹ to R ⁶ are independently selected from C ₁ to C ₅ alkyl, C ₅ to C ₇ cycloalkyl, phenyl or naphthyl. The method of claim 3, wherein A light emitting compound, characterized in that it is selected from the following compounds.

An electroluminescent device comprising an electroluminescent compound according to any one of claims 1 to 4. The method of claim 5, wherein The electroluminescent device using the electroluminescent compound as a dopant material of the light emitting layer.

Images