KR101423375B1 - Tetrakis phenyl compounds for organic electroluminescent device - Google Patents

Abstract

(상기 식에서,
Z는 탄소원자 또는 규소원자이고,
W는 산소원자 또는 황원자이고,
Ar₁, Ar₂, Ar₃, Ar₄는 각각 독립적으로, 치환되지 않거나 C₁~C₁₅의 직쇄 또는 측쇄 알킬기로 치환된 페닐기; 치환되지 않거나 C₁~C₁₅의 직쇄 또는 측쇄 알킬기로 치환된 비페닐기; 치환되지 않거나 C₁~C₁₅의 직쇄 또는 측쇄 알킬기로 치환된 플루오렌기이고,
R_1a, R_1b, R_1c, R_1d, R_2a, R_2b, R_2c, R_2d, R_3a, R_3b, R_3c, R_3d, R_4a, R_4b, R_4c, R_4d는 각각 독립적으로 수소원자 또는 C₁~C₁₅의 직쇄 또는 측쇄 알킬이고,
o,p,q,r 은 각 고리의 치환 갯수로서 각각 독립적으로 0 내지 4의 정수이고, 치환수가 복수개인 경우 각 치환기는 동일하거나 상이하고,
s,t,u,v 는 각 고리의 치환 갯수로서 각각 독립적으로 0 내지 3의 정수이고, 치환수가 복수개인 경우 각 치환기는 동일하거나 상이하다.)The present invention provides a compound for an organic electroluminescence device represented by the following general formula (I).
(I)

(Wherein,
Z is a carbon atom or a silicon atom,
W is an oxygen atom or a sulfur atom,
Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted by a C ₁ to C ₁₅ linear or branched alkyl group; A biphenyl group which is unsubstituted or substituted with a linear or branched alkyl group having ₁ to ₁₅ carbon atoms; A fluorene group which is unsubstituted or substituted with a C ₁ -C ₁₅ linear or branched alkyl group,
_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently a hydrogen atom or a C ₁ ~ C ₁₅ straight or branched chain alkyl,
o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,
s, t, u, and v are the number of substitution of each ring, and each independently is an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)

Description

TECHNICAL FIELD [0001] The present invention relates to a tetrakisphenyl-based organic compound for the production of an organic electroluminescent device,

TECHNICAL FIELD The present invention relates to a compound used in the production of an organic electroluminescent device, and more particularly to a tetrakisphenyl-based organic compound useful as a light emitting layer material.

An organic electroluminescent device refers to a self-emitting organic material that emits light when a current flows through a fluorescent organic compound, and is also referred to as an organic light emitting diode (OLED).

OLEDs are excellent in properties such as reaction speed (response speed), luminance, viewing angle, contrast, power consumption, etc., compared to LCD (Liquid Crystal Display) and PDP (Plasma Display Panel) I have received. In the early days, it was developed as a passive matrix OLED (PMOLED), and it was mass produced as a small display device such as a mobile phone. However, it is in the process of mass production of an active matrix OLED (AMOLED).

The electroluminescence phenomenon of OLEDs was first found in anthracene crystals by Pope, Kallmann, and Magnete in 1963, but it required a high driving voltage of 400V or more, and the luminous efficiency (about 0.05% or less) was very low.

1987 CW Tang and VanSlyke SA is a tris-8 (tetrahydro-quinoline) Aluminum (Alq ₃₎ emission layer, and an electron anode and Mg-Ag alloy with a diamine between the anode as a hole transport layer (HTL), and a green organic light emitting material Transport layer with a thickness of about 50 nm and developed a green OLED device that exhibits luminance of over 1,000 cd / m ² and high luminescence efficiency of 1.5 lm / W even at a driving voltage of 10 V or less (CW Tang, 1986, 49, 1210, 1987, 51, 913; A. Tsumura, et al., App. Phys. Lett. 1986, 48, 183; CW Tang and SA VanSlyke, ). The above-described method shows the possibility of developing a high-brightness, high-efficiency next-generation display, and has been used as a typical OLED manufacturing technique to date.

Today, OLEDs are formed in a multi-layer structure as in FIGS. 1 and 2. The OLED includes a cathode, an electron injection layer (EIL), an electron transfer layer (ETL), an emission material layer (EML), a hole transport layer (HTL) A hole injection layer (HIL), an anode, and a transparent substrate (Glass). When power is supplied, electrons in the cathode migrate to the emission material layer (EML), which is an organic material, with the help of an electron transfer layer (ETL) (EML) with the help of a hole transport layer (HTL) to recombine electrons and holes in the light emitting layer to form an exciton and to excite the excitons to a ground state The energy released during the transition is converted to light of a specific wavelength and emitted.

The desirable properties of all the materials used in OLEDs are that they must have a suitable molecular weight to enable vacuum deposition and exhibit high thermal stability at the glass transition temperature (T _g ) and pyrolysis temperature (T _d ) ) It should be amorphous so that the device will not be destroyed by the crystallization caused by the heat and good adhesion to the adjacent layer should not be transferred to the other layer.

The light emitting layer material for OLED is divided into a fluorescent material derived from a single anti-excitation state and a phosphorescent material derived from a triplet exciton, and can be classified into a light emitting material such as blue, green, and red depending on a luminescent color. The color and color purity of the organic semiconductor light emitting material are determined by the band gap. The band gap is 2.75 eV around the wavelength of 450 nm, the wavelength around 2.4 eV is around 510 nm, Around 2.0 eV is emitted in red with a light wavelength of around 620 nm. The light emitting layer material is divided into a host material and a guest material (hereinafter referred to as Dopant). It is possible to emit light by only the substance of each host or dopant, but its efficiency and luminance are very low due to self-quenching phenomenon, and each molecule is not a characteristic inherent to each molecule due to the self-packing phenomenon among the molecules. Since excimer (excited dimer) characteristics are exhibited, a dopant is doped into a host to enhance luminescence efficiency and device stability. The properties required for the host material must first have excellent charge transport properties. It is necessary to move the holes and electrons in the light emitting layer, so that the mobility is appropriately required. In addition, the host material must transfer energy to the dopant, so that the emission spectrum of the host should be well overlapped with the absorption spectrum of the dopant to cause energy transfer. In terms of energy, the band gap of the host should be wider than the gap of the dopant, and the LUMO level of the host should be higher than the LUMO of the dopant. In addition, there is no crystallinity and it should be uniform. As the characteristics required for the dopant, the EL efficiency must be very high, so that the photoluminescence should be basically high. It should also be well dispersed to the host and not create an exciplex like the host.

Currently widely used fluorescent host materials are shown below. Known as a typical host material, a metal complex system such as Alq ₃ is widely known as a host material of red or green, and a DPVBi derivative is widely used as a blue host material.

Representative fluorescent dopant materials are shown below.

< Green Fluorescent Dopant  >

< Red Fluorescent Dopant  >

< Blue Fluorescent Dopant  >

The present invention is to provide a tetrakisphenyl blue light emitting material having good UV absorption, light emission, HOMO-LUMO band gap and high thermal stability.

The present invention also provides an organic electroluminescent device comprising a light emitting layer formed from the above compound.

The present invention provides a compound for an organic electroluminescence device represented by the following general formula (I).

(I)

(Wherein,

Z is a carbon atom or a silicon atom,

W is an oxygen atom or a sulfur atom,

Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted by a C ₁ to C ₁₅ linear or branched alkyl group; A biphenyl group which is unsubstituted or substituted with a linear or branched alkyl group having ₁ to ₁₅ carbon atoms; A fluorene group which is unsubstituted or substituted with a C ₁ -C ₁₅ linear or branched alkyl group,

_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently a hydrogen atom or a C ₁ ~ C ₁₅ straight or branched chain alkyl,

o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,

s, t, u, and v are the number of substitution of each ring, and each independently is an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)

The compound of formula (I) may preferably be used as a light emitting layer material.

The alkenyl group in the above formula (I) preferably has an E-type structure.

The tetrakisphenyl organic compound according to the present invention has a high T _d value (313 to 410 ° C.) and has thermal stability required for an organic electroluminescent device. The maximum absorption at 371 to 381 nm and the maximum emission at 450 to 466 nm , And HOMO-LUMO band gap at 2.92 ~ 2.99 eV, it can be used as a blue light emitting material for OLED.

1 is a schematic view showing a multilayer structure of an organic electroluminescent device.
2 is a schematic diagram showing the principle of luminescence of an organic electroluminescent device.
3 is (a) ¹ H NMR and (b) ¹³ C NMR spectral data of Compound 10a prepared according to Example 1. Fig.
4 is (a) ¹ H NMR and (b) ¹³ C NMR spectral data of Compound 10b prepared according to Example 2. Fig.
5 is (a) ¹ H NMR and (b) ¹³ C NMR spectral data of Compound 10c prepared according to Example 3. Fig.
6 is (a) ¹ H NMR and (b) ¹³ C NMR spectral data of Compound 10d prepared according to Example 4. Fig.
7 is (a) ¹ H NMR and (b) ¹³ C NMR spectral data of Compound 10e prepared according to Example 5. FIG.
8 is (a) ¹ H NMR and (b) ¹³ C NMR spectral data of Compound 10f prepared according to Example 6.
9 is (a) DSC, (b) TGA spectrum data of the compound 10a prepared according to Example 1. Fig.
10 is (a) DSC, (b) TGA data of compound 10b prepared according to Example 2. Fig.
11 is (a) DSC, (b) TGA data of Compound 10c prepared according to Example 3.
12 is (a) DSC, and (b) TGA data of compound 10d prepared according to Example 4. Fig.
13 is (a) DSC, (b) TGA data of Compound 10e prepared according to Example 5.
14 is (a) DSC, and (b) TGA data of Compound 10f prepared according to Example 6. Fig.
15 is UV absorption and photoluminescence spectral data of Compound 10a prepared according to Example 1. Fig.
16 is UV absorption and photoluminescence spectral data of the compounds 10b, 10c, and 10d prepared according to Examples 2 to 4. FIG.
17 is UV absorption and photoluminescence spectral data of the compounds 10e and 10f prepared according to Examples 5 and 6. FIG.
FIG. 18 is a cyclic voltammogram (CV) data of the compounds 10a, 10b, 10c, 10d, 10e and 10f prepared according to Examples 1 to 6.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have completed the present invention by confirming that a specific arylamine derivative in which a tetrakis spirocyanide structure compound and an 9-phenylcarbazole derivative are amine-bonded can be usefully used as an organic electroluminescent device, .

The present invention provides a compound for an organic electroluminescence device represented by the following general formula (I).

(I)

(Wherein,

Z is a carbon atom or a silicon atom,

W is an oxygen atom or a sulfur atom,

Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted by a C ₁ to C ₁₅ linear or branched alkyl group; A biphenyl group which is unsubstituted or substituted with a linear or branched alkyl group having ₁ to ₁₅ carbon atoms; A fluorene group which is unsubstituted or substituted with a C ₁ -C ₁₅ linear or branched alkyl group,

_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently a hydrogen atom or a C ₁ ~ C ₁₅ straight or branched chain alkyl,

o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,

s, t, u, and v are the number of substitution of each ring, and each independently is an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)

The compound of formula (I) may preferably be used as a blue light emitting layer material.

In the formula (I), W is preferably an oxygen atom, Z is preferably a carbon atom, and the alkene group preferably has an E-type structure.

Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are preferably the same and have a phenyl group, o-toluyl group, m-toluyl group, p-toluyl group or 4-biphenyl group.

In _{addition, R 1a, R 1b, R} 1c, R 1d are the _{same, R 2a, R 2b, R} 2c, R 2d are the _{same, R 3a, R 3b, R} 3c, R 3d are the same, R _4a, R _4b, R _4c and R _4d are preferably the same symmetric structure. Wherein _{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d is PL It does not significantly affect the value. The substituent is preferably a hydrogen atom or a C ₁ to C ₁₅ linear or branched alkyl.

The compound of formula (I) can be synthesized according to the following reaction formula (1). However, the following Reaction Scheme I illustrates a preferred synthesis method and may be produced by a combination of known synthesis methods.

[Reaction Scheme 1]

Compound a and compound b are subjected to a wittig reaction under an organic solvent and acid conditions to synthesize compound c.

The compound c thus prepared is reacted with a primary amine compound (compound d) to synthesize a compound e. In this case, in order to prevent two Ar from being bonded to the primary amine, the compound d is preferably used in an amount of at least 1.3 equivalents based on the compound c.

The above-prepared secondary amine compound (Compound e) is reacted with tetrakis (4-bromophenyl) methane or tetrakis (4-bromophenyl) silane to synthesize the above Formula I. [

At this time, when a single species of the compound e is used, a tetrakis compound having a symmetrical structure is produced. When a plurality of compounds e are mixed and reacted with the compound f, an asymmetric tetrakis compound is produced.

The compound of formula (I) preferably has a symmetrical structure in the synthesis process.

Hereinafter, the present invention will be described in detail with reference to examples.

The NMR, LC-MS, CV, DSC, TGA, UV, and PL spectra of the reactants and products in the following examples were measured using a JEOL NMR 400 Spectrometer, a BRUKER NMR 400 Spectrometer, an Agilent 1200 LC / MS, an Agilent 6130 Quadruple LC / epsilon cyclic voltammetry, Mettler Toledo DSC 1, SDT Q600, Perkin-Elmer Lambda 2S UV-visible spectrometer and Perkin LS Fluorescence Spectrometer. The reagents required for synthesis were Aldrich, TCI and Alfa Aesar GR grade reagents without further purification.

Example  1: 4,4 ', 4' ', 4' '' - Methanetetrayltetrakis (N- (4 - ((E) -2- furan -2-yl) vinyl) phenyl) -N-phenylaniline (Compound 10a)

Synthesis was carried out according to Reaction Scheme 2 below.

[Reaction Scheme 2]

A. Tetrakis (4- Bromophenyl ) methane &lt; / RTI &gt; synthesis (Compound 2)

Tetraphenylmethane (Compound 1 , 5.0 g, 15.6 mmol) and Bromine (19.9 g, 124.8 mmol) were added to carbon tetrachloride (50 ml) and refluxed for 12 hours. After the reaction was completed, the solvent was distilled off under vacuum, and then ethanol was added to crystallize. The filtered product at room temperature was purified by filtration in ethanol: chloroform (1: 1 v / v 200 ml) to obtain 6.6 g of the title compound as an oily product : 66.5%)

^{1 H NMR (400 MHz, CDCl} 3): δ 7.39 (d, 8H J = 8.8Hz) 7.00 (d, 8H J = 8.8Hz)

B. 4- Bromobenzaldehyde Synthesis (Compound 4)

Grignard reagent was prepared by dissolving 1,4-Dibromobenzene (Compound 3, 15.0 g, 635.8 mmol) in dry THF (150 ml), adding Mg (1.5 g, 635.8 mmol) and stirring at 40 to 50 ° C., , DMF (24 ml) was added, and the mixture was stirred at room temperature. When the reaction is complete, excess purified water is added, extracted with EA and washed with aqueous NH ₄ Cl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. The resulting solid was subjected to vacuum distillation at 120 to 130 DEG C to obtain 7.5 g of the title compound as a white solid (Yield: 63.8%).

^{1 H NMR (400 MHz, CDCl} 3): δ 9.97 (s, 1H), 7.76 (d, 2H, J = 8.4), 7.70 (d, 2H, J = 8.4)

C. 2- Methylfuran TPP salt  Synthesis (Compound 6)

2-Methylfuran (Compound 5, 10.0 g, 121.8 mmol) was dissolved in EA (100 ml), N-Bromosuccinimide (22.7 g, 127.9 mmol) was added thereto and stirred at 55 to 60 ° C for 2 hours. When the reaction is completed, the reaction mixture is cooled to 10 to 15 ° C and filtered to remove solid byproducts. Triphenylphosphine (31.9 g, 121.8 mmol) was added to the filtered solution, and the mixture was heated and refluxed for 3 hours. After completion of the reaction, the reaction mixture was cooled to 10 to 15 DEG C and filtered to obtain 48.0 g of the title compound as an oily product (yield: 93.1%).

^{1 H NMR (400 MHz, CD} 3 OD): δ 7.89 (m, 3H), 7.68 (m, 15H), 7.42 (t, 1H, J = 2.0Hz), 6.36 (d, 1H, J = 3.2Hz) , 6.18 (t, IH), 5.12 (d, 2H, J = 14.0 Hz)

D. (E) -2- (4- Bromostyryl ) furan Synthesis (Compound 7)

Methylfuran TPP salt (compound 6, 28.6 g, 67.5 mmol) obtained in step (C) and 4-bromobenzaldehyde (compound 4, 11.9 g, 64.3 mmol) obtained in step (B) And the temperature is cooled to -15 to -10 ° C. After the addition of NaH (4.6 g, 115.0 mmol), the mixture was stirred at -15 to -10 ° C for 1 hour, slowly warmed to room temperature and stirred. When the reaction is complete, quench the excess amount of purified water and filter it to obtain crude (E) -2- (4-Bromostyryl) furan. The dried compound was separated and concentrated by using a Silicagel column (Eluent solution: Toluene), and then recrystallized from ethanol to obtain 6.9 g of the title compound as a pale solid (yield: 43.2%).

^{1 H NMR (400 MHz, CDCl} 3): δ7.45 (m, 2H), 7.41 (d, 1H, J = 2.0Hz), 7.32 (m, 2H), 6.96 (d, 1H, J = 16.4Hz) , 6.87 (d, 1H, J = 16.4Hz), 6.43 (q, 1H, J = 3.2, 2.0Hz), 6.37 (d, 1H, J = 3.2Hz)

E. Preparation of (E) -4- (2- ( furan -2- yl ) vinyl ) -N- phenylaniline (Compound 9a)

(Compound 8a, 16.1 g, 173.4 mmol) and t-BuONa (8.0 g, 83.5 mmol) obtained in the above step (D) were added to a solution of (E) -2- (4-Bromostyryl) furan mmol) are added to toluene (160 ml), and the mixture is stirred at a temperature of 40 to 45 ° C. Pd (dba) ₂ (2.22 g, 3.8 mmol) was added at a temperature of 40 to 45 ° C, the temperature was raised to 60 to 65 ° C, and the mixture was stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (1.3 g, 3.2 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed twice with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. The obtained solid was separated and concentrated by using a Silicagel column (eluent solution: toluene) and recrystallized with n-Heptane to obtain 13.6 g of the title compound as a yellow solid (yield: 81.2%).

^{1 H NMR (400 MHz, CDCl} 3): δ7.37 (m, 3H), 7.29 (m, 2H), 7.04 (m, 6H), 6.77 (d, 1H, J = 16.0Hz), 6.41 (dd, 1H, J = 3.2, 2.0Hz) , 6.30 (d, 1H, J = 3.2Hz), 5.79 (s, 1H)

F. 4,4 ', 4' ', 4' '' - Methanetetrayltetrakis (N- (4 - ((E) -2- furan -2-yl) vinyl) phenyl) -N-phenylaniline (Compound 10a)

Tetrakis (4-Bromophenyl) methane (Compound 2 , 1.00 g, 1.57 mmol) obtained in the above step (A) and (E) -4- (2- (furan- 2- N-phenylaniline (compound 9a, 1.64 g, 6.29 mmol) and t-BuONa (0.79 g, 8.18 mmol) were added to 30 ml of toluene and stirred at 40 to 45 ° C. Pd (dba) ₂ (0.21 g, 0.38 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.12 g, 0.31 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed once with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. Separate the obtained solid with a Silicagel column (Eluent solution: toluene). The separated toluene solution was passed through a neutral aluminum oxide column (Eluent solution: toluene) and then recrystallized with n-Heptane to obtain 1.6 g of the title compound as an ocher-colored solid (yield: 75.1%).

¹ H NMR (400 MHz, CDCl ₃ ):? (Ppm) 7.38-6.95 (m, 60H), 6.77 (d, 4H), 6.41 (q, 4H), 6.30 (d, 4H); ¹³ C NMR (400 MHz, CDCl ₃ ):? (Ppm) 153.59, 147.44, 147.21, 145.33, 141.89, 141.27, 131.99, 131.32, 129.37, 127.24, 126.71, 124.80, 123.81, 123.22, 122.59, 115.05, 111.67, 107.99 , 63.17; LC / MS APCI + MM-ES Positive: Calcd. For C ₉₇ H ₇₃ N ₄ O ₄ (MH ^&lt; ⁺ & gt ^; ) m / z 1357.5, Found: 1357.5

Example  2: 4,4 ', 4' ', 4' '' - Methanetetrayltetrakis (N- (4 - ((E) -2- furan -2- yl ) vinyl ) phenyl ) -N-o-tolylaniline (Compound 10b)

Synthesis was carried out according to Reaction Scheme 3 below.

[Reaction Scheme 3]

E. (E) -N- (4- (2- ( furan -2- yl ) vinyl ) phenyl )-2- methylaniline (Compound 9b)

(E) -2- (4-Bromostyryl) furan (Compound 7, 11.0 g, 44.1 mmol), o-Toluidine (Compound 8b, 8.0 g, 75.0 mmol) obtained in the step (D) (6.3 g, 66.2 mmol) were added to toluene (165 ml), and the mixture was stirred at 40 to 45 ° C. Pd (dba) ₂ (1.52 g, 2.6 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.89 g, 2.2 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed twice with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. The obtained solid was separated and concentrated by using a Silicagel column (eluent solution: toluene) and recrystallized with n-Heptane to obtain 10.1 g of the title compound as a yellow solid (yield: 83.0%).

^{1 H NMR (400 MHz, CDCl} 3): δ7.36 (m, 3H), 7.27 (m, 1H), 7.20 (d, 1H, J = 7.6Hz), 7.16 (t, 1H, J = 7.6Hz) , 6.59 (m, 4H), 6.76 (d, 1H, J = 16.4Hz), 6.40 (q, 1H, J = 3.2, 2.0Hz), 6.28 (d, 1H, J = 2.8Hz), 5.46 (s, 1H), 2.26 (s, 3H)

F. 4,4 ', 4' ', 4' '' - Methanetetrayltetrakis (N- (4 - ((E) -2- furan -2-yl) vinyl) phenyl) -N-o-tolylaniline) (Compound 10b)

Example 1 (A) Tetrakis (4- Bromophenyl) obtained in step methane (compound 2, 1.00g, 1.57mmol), the (E) BSF o-Toluene (compound 9 b, 1.73g obtained in step, 6.29mmol of ) And t-BuONa (0.79 g, 8.18 mmol) were charged in toluene (30 ml), and the mixture was stirred at 40 to 45 ° C. Pd (dba) ₂ (0.21 g, 0.38 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.12 g, 0.31 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed once with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. Separate the obtained solid with a Silicagel column (Eluent solution: toluene). The separated toluene solution was concentrated by passing through a neutral aluminum oxide column (Eluent solution: toluene) and recrystallized with n-Heptane to obtain 1.17 g of the title compound as an ocher-colored solid (yield: 52.7%).

^{1 H NMR (400 MHz, CDCl} 3): δ (ppm) 7.29 ~ 6.85 (m, 56H), 6.73 (d, 4H), 6.39 (q, 4H), 6.28 (d, 4H), 2.02 (s, 12H ); ¹³ C NMR (400 MHz, CDCl ₃ ):? (Ppm) 153.74, 146.93, 145.03,144.74,141.76,141.49,136.60,131.83,129.95,129.69,127.49,127.16,126.93,126.28,121.01,201.44,114.44,111.65 , 1107.68, 62.93, 18.69; LC / MS APCI + MM-ES Positive: Calcd. For C ₁₀₁ H ₈₁ N ₄ O ₄ (MH ⁺ ) m / z 1413.6, Found: 1413.6

Example  3: 4,4 ', 4' ', 4' '' - Methanetetrayltetrakis (N- (4 - ((E) -2- furan -2- yl ) vinyl ) phenyl ) -N-m-tolylaniline) (Compound 10c)

Synthesis was carried out according to Reaction Scheme 4 below.

[Reaction Scheme 4]

E. (E) -N- (4- (2- ( furan -2- yl ) vinyl ) phenyl ) -3- methylaniline (Compound 9c)

Toluene (compound 8c, 5.8 g, 54.2 mmol) and t-BuONa (5.2 g, 54.2 mmol) were added to a solution of (E) -2- (4-Bromostyryl) furan 135 ml) and stirred at a temperature of 40 to 45 ° C. Pd (dba) ₂ (1.25 g, 2.1 mmol) was added at a temperature of 40 to 45 ° C, the temperature was raised to 60 to 65 ° C, and the mixture was stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.73 g, 1.8 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed twice with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. The obtained solid was separated and concentrated by using a Silicagel column (eluent solution: toluene) and recrystallized with n-Heptane to obtain 11.0 g of the title compound as a yellow solid (yield: 82.9%).

^{1 H NMR (400 MHz, CDCl} 3): δ7.37 (m, 3H), 7.17 (m, 1H), 6.90 (m, 5H), 6.77 (d, 1H, J = 16.0Hz), 6.41 (q, 1H, J = 3.2, 2.0Hz) , 6.29 (d, 1H, J = 3.2Hz), 5.75 (b, 1H), 2.32 (s, 3H)

F. 4,4 ', 4' ', 4' '' - Methanetetrayltetrakis (N- (4 - ((E) -2- furan -2-yl) vinyl) phenyl) -N-m-tolylaniline (Compound 10c)

A Tetrakis (4-Bromophenyl) methane (compound 2, 1.00g, 1.57mmol) and m-BSF Toluene (compound 9 c, 1.73g, 6.29mmol) and t-BuONa (0.79g, 8.18mmol) in Toluene (30ml) And the mixture is stirred at a temperature of 40 to 45 ° C. Pd (dba) ₂ (0.21 g, 0.38 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.12 g, 0.31 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed once with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. Separate the obtained solid with a Silicagel column (Eluent solution: toluene). The separated toluene solution was concentrated by passing through a neutral aluminum oxide column (Eluent solution: toluene) and recrystallized with n-Heptane to obtain 0.8 g of the title compound as an ocher-colored solid (yield: 36.0%).

^{1 H NMR (400 MHz, CDCl} 3): δ (ppm) 7.37 ~ 6.85 (m, 56H), 6.77 (d, 4H), 6.40 (q, 4H), 6.29 (d, 4H), 2.26 (s, 12H ); ¹³ C NMR (400 MHz, CDCl ₃ ):? (Ppm) 153.63, 147.35, 145.37, 141.86, 141.18, 139.25, 132.41, 131.96, 131.09, 129.20, 127.20, 126.76, 125.68, 124.29, 123.64, 122.47, 122.24, 114.95 , 111.65, 107.91, 63.16, 21.50; LC / MS APCI + MM-ES Positive: Calcd. For C ₁₀₁ H ₈₁ N ₄ O ₄ (MH ⁺ ) m / z 1413.6, Found: 1413.6

Example  4: 4,4 ', 4', 4 '' - Methanetetrayltetrakis (N- (4 - ((E) -2- furan -2- yl ) vinyl ) phenyl ) -N-p-tolylaniline) (Compound 10d)

The synthesis was carried out according to Reaction Scheme 5 below.

[Reaction Scheme 5]

E. (E) -N- (4- (2- ( furan -2- yl ) vinyl ) phenyl )-2- methylaniline (Compound 9d)

BuONa (6.3 g, 66.2 mmol) and p-Toluidine (Compound 8d, 9.5 g, 88.3 mmol) and (E) -2- (4-Bromostyryl) furan (compound 7, 11.0 g, 44.1 mmol) 165 ml) and stirred at a temperature of 40 to 45 ° C. Pd (dba) ₂ (1.52 g, 2.6 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.89 g, 2.2 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed twice with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. The obtained solid was separated and concentrated by using a Silicagel column (eluent solution: toluene) and recrystallized from n-Heptane to obtain 9.6 g of the title compound as a yellow solid (yield: 78.9%).

^{1 H NMR (400 MHz, CDCl} 3): δ7.35 (m, 3H), 7.03 (m, 7H), 6.75 (d, 1H, J = 16.4Hz), 6.40 (q, 1H, J = 3.4, 2.0 Hz), 6.28 (d, 1H , J = 3.2Hz), 5.70 (s, 1H), 2.31 (s, 3H)

F. 4,4 ', 4' ', 4' '' - Methanetetrayltetrakis (N- (4 - ((E) -2- furan -2-yl) vinyl) phenyl) -N-p-tolylaniline) (Compound 10d)

A Tetrakis (4-Bromophenyl) methane (compound 2, 1.00g, 1.57mmol) and p-Toluene BSF (compound 9 d, 1.73g, 6.29mmol) and t-BuONa (0.79g, 8.18mmol) in Toluene (30ml) And the mixture is stirred at a temperature of 40 to 45 ° C. Pd (dba) ₂ (0.21 g, 0.38 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.12 g, 0.31 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed once with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. Separate the obtained solid with a Silicagel column (Eluent solution: toluene). The isolated toluene solution was concentrated by passing through a neutral aluminum oxide column (eluent solution: toluene) and recrystallized with n-Heptane to obtain 0.9 g of the title compound as an ocher-colored solid (yield: 42.8%).

^{1 H NMR (400 MHz, CDCl} 3): δ (ppm) 7.37 ~ 6.94 (m, 56H), 6.75 (d, 4H), 6.40 (q, 4H), 6.28 (d, 4H), 2.31 (s, 12H ); ¹³ C NMR (400 MHz, CDCl ₃ ):? (Ppm) 153.66, 147.43, 145.40, 144.83, 141.82, 141.02, 133.28, 131.92, 130.80, 130.08, 127.16, 126.82, 125.47, 123.13, 122.16, 114.78, 111.64, , 63.09, 20.93; LC / MS APCI + MM-ES Positive: Calcd. For C ₁₀₁ H ₈₁ N ₄ O ₄ (MH ^&lt; ⁺ & gt ^; ) m / z 1413.6, Found: 1413.6

Example  5: N, N ' , N '' , N '' ' - (4,4 ', 4 &quot;, 4 &quot;' - Methanetetrayltetrakis ( benzene -4,1- diyl )) tetrakis (Synthesis of N- (4 - ((E) -2- (furan-2-yl) vinyl) phenyl) bipenyl-

Synthesis was carried out according to Scheme 6 below.

[Reaction Scheme 6]

E. (E) -N- (4- (2- ( furan -2- yl ) vinyl ) phenyl ) biphenyl -4- amine (Compound 9e)

(E) -2- (4-Bromostyryl) furan ( 11 , 11.0 g, 44.1 mmol), 4-Aminobiphenyl (9.7 g, 57.4 mmol) and t-BuONa (6.3 g, 66.2 mmol) And the temperature is raised to 40 to 45 ° C. Pd (dba) ₂ (1.52 g, 2.6 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.89 g, 2.2 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed twice with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. The obtained solid was separated and concentrated by using a Silicagel column (eluent solution: toluene), and recrystallized with n-Heptane to obtain the title compound (Yield: 77.8%).

^{1 H NMR (400 MHz, CDCl} 3): δ7.55 (m, 4H), 7.41 (m, 5H), 7.31 (m, 1H), 7.16 (m, 2H), 7.08 (m, 2H), 6.99 ( d, 1H, J = 16.0Hz) , 6.78 (d, 1H, J = 16.4Hz), 6.41 (q, 1H, J = 2.0, 3.2Hz), 6.30 (d, 1H, J = 3.6Hz), 5.87 ( s, 1 H)

F. N, N ', N' ', N''- (4,4', 4 '', 4 '' - methanetetrayltetrakis (benzene- diyl )) tetrakis (N- (4 - ((E) -2- ( furan -2- yl ) vinyl ) phenyl ) bipenyl -4-aniline) (Compound 10e)

Toluene (30 ml) was charged with Tetrakis (4-Bromophenyl) methane (Compound 2 , 1.00 g, 1.57 mmol) and BSF p-Biphenyl (Compound 8e, 2.12 g, 6.29 mmol) and t-BuONa (0.79 g, 8.18 mmol) And the temperature is raised to 40 to 45 ° C. Pd (dba) ₂ (0.21 g, 0.38 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.12 g, 0.31 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed once with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. Separate the obtained solid with a Silicagel column (Eluent solution: toluene). The separated toluene solution was concentrated by passing through a neutral aluminum oxide column (eluent solution: toluene) and recrystallized with n-Heptane to obtain 0.9 g of the title compound as an ocher-colored solid (yield: 36.4%).

^{1 H NMR (400 MHz, CDCl} 3): δ (ppm) 7.48 ~ 7.05 (m, 72H), 6.98 (d, 4H), 6.78 (d, 4H), 6.40 (q, 4H), 6.29 (d, 4H ); ¹³ C NMR (400 MHz, CDCl ₃ ):? (Ppm) 153.57, 147.02,146.75,145.26,141.95,141.47,141.58,135.72,138.09,131.63,128.84,127.95,127.34,127.12,126.97,126.68,124.65,124.13 , 122.86, 115.23, 111.70, 108.12, 63.30; LC / MS APCI Positive: Calcd. For C ₁₂₁ H ₈₉ N ₄ O ₄ (MH ^&lt; ⁺ & gt ^; ) m / z 1661.6, Found: 1661.6

Example  6: N, N ' , N '' , N '' ' - (4,4 ', 4 &quot;, 4 &quot;' - Methanetetrayltetrakis ( benzene -4,1- diyl )) tetrakis (Synthesis of N- (4 - ((E) -2- (furan-2- yl) vinyl) phenyl) -9,9-dimethyl-9H-fluoren-

Synthesis was carried out according to Scheme 7 below.

[Reaction Scheme 7]

E. (E) -N- (4- (2- ( furan -2- yl ) vinyl ) phenyl ) -9,9- dimethyl -9H-fluoren-2-amine (Compound 9f)

(Compound 8f, 10.9 g, 52.2 mmol) and t-BuONa (5.8 g, 44.2 mmol) were added to a solution of (E) -2- (4-Bromostyryl) furan 60.2 mmol) is added to toluene (150 ml), and the mixture is stirred at a temperature of 40 to 45 ° C. Pd (dba) ₂ (1.38 g, 2.4 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.81 g, 2.0 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed twice with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. The obtained solid was separated and concentrated by using a Silicagel column (eluent solution: toluene) and recrystallized with n-Heptane to obtain 11.9 g of the title compound as an ocher-colored solid (yield: 78.5%).

^{1 H NMR (400 MHz, CDCl} 3): δ 7.63 (m, 2H), 7.40 (m, 4H), 7.28 (m, 3H), 7.18 (d, 1H, J = 2.0Hz), 7.07 (m, 2H ), 7.01 (d, 1H, J = 30.4Hz), 6.78 (d, 1H, J = 16.4Hz), 6.41 (q, 1H, J = 3.2, 2.0Hz), 6.30 (d, 1H, J = 3.2Hz ), 5.91 (b, 1 H), 1.47 (s, 6 H)

F. N, N ', N' ', N''- (4,4', 4 '', 4 '' - methanetetrayltetrakis (benzene- diyl )) tetrakis (N- (4 - ((E) -2- ( furan -2- yl ) vinyl ) phenyl ) -9,9-dimethyl-9H-fluoren-2-amine) (Compound 10f)

Toluene (30 ml) was charged with Tetrakis (4-Bromophenyl) methane (Compound 2 , 1.00 g, 1.57 mmol) and BSF 2DM Fluorene (Compound 9 f , 2.37 g, 6.29 mmol) and t-BuONa (0.79 g, 8.18 mmol) And the temperature is raised to 40 to 45 ° C. Pd (dba) ₂ (0.21 g, 0.38 mmol) is added at a temperature of 40 to 45 ° C, the temperature is raised by 60 to 65 ° C, and the mixture is stirred for 0.5 hours. Then, tri-tert-butylphosphine 50% toluene solution (TTBuP-50T) (0.12 g, 0.31 mmol) was added thereto and stirred at 80 to 90 ° C for 3 hours to terminate the reaction. Cool to room temperature, quench with excess of purified water, and extract with toluene. The organic layer is washed once with 3.5% aqueous HCl solution. The obtained organic layer was treated with MgSO ₄ and concentrated in vacuo to obtain a solid. Separate the obtained solid with a Silicagel column (Eluent solution: toluene). The separated toluene solution was passed through a neutral aluminum oxide column (Eluent solution: toluene) and then recrystallized with n-Heptane to obtain 1.3 g of the title compound as an ocher-colored solid (yield: 45.3%).

¹ H NMR (400 MHz, CDCl ₃ ):? (Ppm) 7.34-7.05 (m, 64H), 6.98 (d, 4H) ); ¹³ C NMR (400 MHz, CDCl ₃ ):? (Ppm) 155.21,153.62,147.36,146.85,145.55,141.91,141.37,138.92,134.71,132.04,131.18,127.27,127.07,126.73,126.67,124.01,123.52,122.67 , 122.57, 120.76, 119.56, 119.36, 115.03, 111.68, 108.00, 63.01, 46.90, 27.16; LC / MS APCI Positive: Calcd. For C ₁₃₃ H ₁₀₅ N ₄ O ₄ (MH ^&lt; ⁺ & gt ^; ) m / z 1821.8, Found: 1822.8

Experimental Example  One : DSC ( Differential scanning calorimeter ) And TGA (Thermogravimetry) evaluation

DSC was measured at a rate of 10 K / min from 50 to 400 ° C for the compounds 10a to 10f obtained in Examples 1 to 6, and TGA was measured at a rate of 10 K / min from 50 to 800 ° C. The results are shown in FIGS. And the measurement result values are summarized in Table 1 below.

Fig. 9 is a graph showing the relationship between the compound 10a (Example 1), Fig. 10 showing the compound 10b (Example 2), Fig. 11 showing the compound 10c (Example 3) Example 5), FIG. 14 is (a) DSC, and (b) TGA spectral data of Compound 10d (Example 6).

Example compound T _g (° C) T _m (° C) T _d (° C) T _onset (° C) Example  One Compound 10a - 200 404 504.18 Example  2 Compound 10b - 245 410 465.84 Example  3 Compound 10c - 150 313 432.90 Example  4 Compound 10d - 149 408 512.09 Example  5 Compound 10e - 150 391 520.96 Example  6 Compound 10f - 183 355 500.43

In the DSC graphs shown in Figs. 9 to 14, the T _g value was not shown because the molecular weight was large, and the T _m value was not clearly displayed. However, if the T _m value was set, the temperature was measured at 149 to 245 ° C.

TGA measurements T _d value (5% weight decrease compared points) of the compounds of the invention was observed in 313 ~ 410 ℃. Also, the tangent (T _onset ) at the baseline and inflection point was normally measured as the decomposition temperature and was measured at a significantly high temperature of 432-520 ° C. Compound 10c and compound 10f show abrupt weight change below 200 DEG C, which appears to be caused by residual solvent. Compound 10c is determined to be due to impurities exhibit low T _d value, compared to other compounds.

As a result of the measured TGA, DSC (not shown in general), the compounds according to the present invention were found to have high thermal stability to be usefully used in OLED devices.

Experimental Example  2: UV , PL , CV  evaluation

The compounds obtained in Examples 1 to 6 were dissolved in CHCl ₃ to measure a UV absorption spectrum at a concentration of 0.01 mM and a PL spectrum at a concentration of 0.1 mM to measure the photoluminescence spectrum. And measurement results are summarized in Table 2 below.

CV measurement was performed using 0.1 M Tetraethylammonium tetrafluoroborate and MC solvent as the electrolyte, and the sample was diluted to a concentration of 0.5 mM. Pt electrode and Ag / AgCl electrode were used as a counter electrode and a reference electrode in a working electrode, and the same reference electrode was used in the same electrolyte solution to measure ferrocene. 18, and the measurement result values are summarized in Table 2 below.

FIG. 15 shows the UV absorption and photoluminescence spectrum data of the compound 10a, FIG. 16 shows the compounds 10b, 10c and 10d, and FIG. 17 shows the spectra data of the compounds 10e and 10f.

18 is a cyclic voltammogram (CV) data of the compounds 10a, 10b, 10c, 10d, 10e and 10f.

Example
compound UV  λ _max
( nm ) PL  λ _max
( nm ) HOMO
( eV ) LUMO
( eV ) HOMO - LUMO
Energy  gap
( eV ) Example  One Compound 10a 378 454 -5.05 -2.07 2.99 Example  2 Compound 10b 378 450 -5.05 -2.05 2.99 Example  3 Compound 10c 379 451 -5.03 -2.09 2.94 Example  4 Compound 10d 381 455 -5.03 -2.08 2.95 Example  5 Compound 10e 377 453 -5.06 -2.09 2.97 Example  6 Compound 10f 371 466 -5.04 -2.12 2.92

As shown in FIGS. 15 to 17, the PL spectral (photoluminescence spectrum) was measured at a concentration of 0.1 mM, the maximum UV absorbance was observed at 371 to 381 nm, and the PL maximum peak was measured at 454 to 466 nm. In the compounds 10a to 10e, the UV and PL values were measured to be almost the same, but in the case of the compound 13f, the benzene ring of the fluorene substituent was in a plane, and the HOMO-LUMO gap became small and PL value deviating from 450 nm was measured.

The measured HOMO-LUMO energy gap was 2.92 ~ 2.99eV. A similar energy gap was measured in both compounds 10a-10f.

From the above results, it was confirmed that the compound according to the present invention can be used as blue fluorescent materials excellent in a fluorescent electroluminescent device.

Claims (10)

A compound for the production of an organic electroluminescent device represented by the following formula (I).
(I)

(Wherein,
Z is a carbon atom or a silicon atom,
W is an oxygen atom or a sulfur atom,
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A biphenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A fluorene group which is unsubstituted or substituted with a methyl group or an ethyl group,
_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently Is a hydrogen atom, a methyl group or an ethyl group,
o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,
s, t, u, and v are the number of substitution of each ring, and each independently is an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)
The method according to claim 1,
A compound for an organic electroluminescence device, which is represented by the following formula (II).
[Formula II]

(Wherein,
Z is a carbon atom or a silicon atom,
W is an oxygen atom or a sulfur atom,
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A biphenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A fluorene group which is unsubstituted or substituted with a methyl group or an ethyl group,
_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently Is a hydrogen atom, a methyl group or an ethyl group,
o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,
s, t, u, and v are the number of substitution of each ring, and each independently is an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)
3. The method of claim 2,
A compound for producing an organic electroluminescent device, which is represented by the following formula (III).
[Formula (III)

(Wherein,
Z is a carbon atom or a silicon atom,
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A biphenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A fluorene group which is unsubstituted or substituted with a methyl group or an ethyl group,
_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently Is a hydrogen atom, a methyl group or an ethyl group,
o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,
s, t, u, and v are the number of substituents in each ring, and are each independently an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)
The method according to claim 1,
A compound for producing an organic electroluminescence device, which is represented by the following formula (IV).
[Formula IV]

(Wherein,
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A biphenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A fluorene group which is unsubstituted or substituted with a methyl group or an ethyl group,
_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently Is a hydrogen atom, a methyl group or an ethyl group,
o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,
s, t, u, and v are the number of substitution of each ring, and each independently is an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)
delete The method according to claim 1,
A compound for producing an organic electroluminescent device, which is represented by the following formula (VI).
(VI)

(Wherein,
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A biphenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A fluorene group which is unsubstituted or substituted with a methyl group or an ethyl group,
_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently Is a hydrogen atom, a methyl group or an ethyl group,
o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,
s, t, u, and v are the number of substitution of each ring, and each independently is an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)
The method according to claim 6,
A compound for producing an organic electroluminescence device, which is represented by the following formula (VII).
[Formula VII]

(Wherein,
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A biphenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A fluorene group which is unsubstituted or substituted with a methyl group or an ethyl group,
_{R 1a, R 1b, R 1c} , R 1d, R 2a, R 2b, R 2c, R 2d, R 3a, R 3b, R 3c, R 3d, R 4a, R 4b, R 4c, R 4d are each independently Is a hydrogen atom, a methyl group or an ethyl group,
o, p, q, and r are the number of substituents in each ring, and are each independently an integer of 0 to 4. When there are a plurality of substitution numbers, the respective substituents are the same or different,
s, t, u, and v are the number of substitution of each ring, and each independently is an integer of 0 to 3. When there are a plurality of substitution numbers, the respective substituents are the same or different.)
8. The method of claim 7,
A compound for the production of an organic electroluminescent device, which is represented by the following formula (VIII).
(VIII)

(Wherein,
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a phenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; A biphenyl group which is unsubstituted or substituted with a methyl group or an ethyl group; Or a fluorene group which is unsubstituted or substituted with a methyl group or an ethyl group.
9. The method of claim 8,
Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are the same and are selected from a phenyl group, o-toluyl group, m-toluyl group, p-toluyl group, 4-biphenyl group and 9,9- Or a substituent.
An organic electroluminescent device comprising a compound according to any one of claims 1 to 4 and 6 to 9 in a light emitting layer.

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