KR20160102949A - Novel compounds for organic electroluminescent device - Google Patents

Abstract

Provided is a compound which is represented by chemical formula 1, and is used to manufacture an organic electroluminescent device. According to the present invention, the compound has high hole mobility, high thermal stability, a high band gap energy, a high energy level between a hole injection layer and a luminous layer, a low LUMO value, non-crystallinity, and the like, thereby being useful to a hole transfer material.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound for organic electroluminescent device,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a compound used in the production of an organic electroluminescent device, and more particularly, to a novel organic compound which can be usefully used as a hole transporting 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 a luminance of more than 1,000 cd / m ² and a 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 characteristics of all the materials used in OLEDs are that they should have a suitable molecular weight to enable vacuum deposition and exhibit high thermal stability at a glass transition temperature (Tg) and a thermal decomposition temperature (Td), and as Joule heat It should be amorphous so that the device is not destroyed by the crystallization caused and the adhesion to the adjacent layer should be good but not to the other layer.

The material used for the hole transport layer (HTL) not only rapidly transports holes injected from the hole injection layer to the light emitting layer, but also bounds electrons in the light emitting layer, thereby increasing the probability of forming an exciton. The hole transporting material preferably has a high hole mobility and has an ionization level between the hole injection layer and the light emitting layer and has a large band gap in order to suppress exciton generation at the interface between the hole transporting layer and the light emitting layer 2). The ability to control electrons from moving from the light emitting layer to the hole transporting layer, and mechanical properties such as heat resistance and durability.

The characteristics of hole transport materials should be summarized as follows.

- High hole mobility

The energy level between the hole injection layer and the light emitting layer

- Low LUMO value for electronic blocking

- Crystalline thin film

- High thermal stability

- High band gap energy

The physical properties required for the hole transporting material are directly related to the lifetime and the high efficiency of the OLED.

Triphenylamine structure is known to have excellent hole mobility, and diamine, triamine, and tetramine derivatives having a triphenylamine structure as a basic skeleton are widely used as hole transport materials. Initially TPD (Triphenyldiamine) was used but its glass transition temperature, which is one of the most important characteristics, was low at 60 ℃, which was weak in terms of thermal stability. In order to improve the thermal stability, derivatives having a larger molecular weight, such as α-NPD, spiro-TTB, etc., have been developed mainly by increasing the chemical unit of the triphenylamine skeleton.

Representative hole transport materials developed are shown below.

As described above, for the long life and high power efficiency of the OLED display, the hole transporting material should have high hole mobility, thermal stability, band gap energy, energy level between the hole injection layer and the light emitting layer, low LUMO value, and amorphous And development of a new material that satisfies these properties is required.

The present invention provides a novel compound having high hole mobility, thermal stability, high band gap energy, energy level between the hole injection layer and the light emitting layer, low LUMO value, and improved physical properties required for hole transport materials such as amorphous have.

Further, the present invention is to provide the novel compound, which is used as a light emitting material if necessary.

The present invention also provides an organic electroluminescent device including a hole transporting layer or a light emitting layer formed from the above compound.

In order to solve the above-mentioned object, the present invention provides a compound for organic electroluminescent device represented by the following general formula (I).

[Chemical Formula 1]

(Wherein,

-Z- represents a single bond _{(-), -CR 5 R 6} -, -CR 5 R 6 -CR 5 R 6 -, -CR 5 = CR 6 -, -O-, -S-,> NR 5 or> C = O,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a C ₁ to C ₁₅ linear or branched alkyl group,

m, n, p, and q are independently the number of substituents of each benzene ring, 0, 1, 2, 3 or 4,

Ar ₁ and Ar ₂ are each independently a phenyl group which is unsubstituted or substituted with 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 by a C ₁ -C ₁₅ linear or branched alkyl group.)

The compound of formula (I) may preferably be used as a hole transporting material.

The novel organic compound according to the present invention has high hole mobility, thermal stability, high band gap energy, energy level between the hole injection layer and the light emitting layer, low LUMO value, amorphous property, etc., .

Therefore, the OLED display using the compound of the present invention has a high power efficiency and a long service life.

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 shows the formula of the compound for organic EL device according to the present invention.

Hereinafter, the present invention will be described in detail.

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

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

(I)

(Wherein,

-Z- represents a single bond _{(-), -CR 5 R 6} -, -CR 5 R 6 -CR 5 R 6 -, -CR 5 = CR 6 -, -O-, -S-,> NR 5 or> C = O,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a C ₁ to C ₁₅ linear or branched alkyl group,

m, n, p, and q are independently the number of substituents of each benzene ring, 0, 1, 2, 3 or 4,

Ar ₁ and Ar ₂ are each independently a phenyl group which is unsubstituted or substituted with 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 by a C ₁ -C ₁₅ linear or branched alkyl group.)

The compound according to the present invention is characterized in that the spirofluorene derivative and the 9-phenylcarbazole derivative are triarylamine derivatives linked by an amine.

In the present invention, the spirofluorene derivative is characterized in that the benzene rings opposite to the fluorene are cyclized to improve the binding stability between the benzene rings, and the cyclization is a single bond (direct bond between benzene) or C ₁ ~ C ₂ alkyl, or combine know alkene group or ketone, characterized in that the bond O, S, N atoms. The cyclization enhances the hole transporting ability, heat resistance and durability of the compound without affecting the conjugated double bond.

The spirofluorene derivatives include spirofluorene, spiro (fluorene-xanthene), spiro (fluorene-9,10-dihydro-10,10-dialkyl anthracene), spiro (fluorene- Dibenzo [a, d] cycloheptene), spiro (fluorene-5H-dibenzo [a, d] cycloheptene), spiro (fluorene-10 -Alkyl-10H-acridine), spiro (fluorene-anthracene-10-one), and the like.

In the present invention, R ₁ to R ₁₁ substituted on the benzene ring are hydrogen atoms or C ₁ to C ₁₅ linear or branched alkyl groups. Since the substituent does not affect the conjugated double bond, there is no significant difference in the basic skeletal structure and hole transporting ability. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, In consideration of the molding stability, it is preferably an alkyl group having ₁ to ₆ carbon atoms, more preferably a hydrogen atom or a methyl group (C ₁ ).

Considering the band gap energy, the energy level and the LUMO value, the sum of the benzene rings of Ar ₁ and Ar ₂ in the formula (I) is preferably 3. That is, when Ar ₁ is a biphenyl group or a derivative thereof, as shown in the following formula (II), Ar ₂ is preferably a phenyl group, and when Ar ₁ is a phenyl group, Ar ₂ is a biphenyl group or derivative thereof .

[Formula II]

[Formula (III)

(Wherein,

-Z- represents a single bond _{(-), -CR 5 R 6} -, -CR 5 R 6 -CR 5 R 6 -, -CR 5 = CR 6 -, -O-, -S-,> NR 5 or> C = O,

The dotted line is absent or -CR < ₁₀ > R < ₁₁ &

Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is independently a hydrogen atom or a C ₁ to C ₁₅ linear or branched Alkyl group,

m, n, p, q, s, and t are independently 0, 1, 2, 3 or 4 and r is 0, 1, 2, 3, 4 or 5,

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, which may be prepared by a combination of other well-known synthetic methods, and the order of the amine reaction is not limited.

[Reaction Scheme 1]

Bromobiphenyl is reacted with a dibenzocycloalkane compound (compound a) after the Grignard reagent is prepared using Mg powder and then reacted under an acidic condition or reacted under n-BuLi (butyl lithium) condition Under an acid condition to synthesize a spirofluorene derivative (compound b).

An amino compound (compound c) is synthesized by reacting the spirofluorene derivative (compound b) prepared above with nitric acid or a mixed acid of nitric acid / sulfuric acid to synthesize an amino compound (compound c) and then hydrogenation reaction under high pressure to synthesize a primary amine compound (compound d).

The thus prepared primary amine compound (compound d) is reacted with Ar ₁ -Br (compound e) to give a secondary amine compound (compound f). In this case, in order to prevent two Ar ₁ from bonding to the primary amine, the compound d is preferably used in an amount of at least 1.3 equivalents based on Ar ₁ -Br.

The desired secondary amine compound (compound f) is reacted with a phenylcarbazole derivative compound (compound g) by an amine to synthesize the desired compound (compound h).

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are intended to illustrate the technical concept of the present invention, and the present invention is not limited to the following examples.

Example 1: N- biphenyl-4-yl -N- (4- (9- phenyl -9H- carbazol-3-yl) phenyl) fluorene RY lobby Synthesis of fluoren-2-amine (compound 5 )

Synthesis was carried out according to Reaction Scheme 2 below.

[Reaction Scheme 2]

(A) Synthesis of 9,9'-spirobifluorene: (Compound 1)

46.4 g (200 mmol) of 2-bromobiphenyl, 5.3 g of magnesium powder and 900 ml of dry THF were placed in a three-necked flask and refluxed for 4 hours. 36.0 g (200 mmol) of fluorenone is dissolved in 300 ml of dry THF, and the solution is slowly added dropwise thereto, followed by refluxing for 2 hours. Cool to about 10 ° C, add 200 ml of 1N HCl, stir for 30 minutes, concentrate THF, add 1000 ml of water, stir and filter. The filtered solid was dissolved in toluene, and the water remaining with MgSO ₄ was removed. 7.0 g of neutral activated carbon was added and stirred for 30 minutes, followed by filtration and concentration. 400 ml of cyclohexane is added to the concentrated residue, stirred for 1 hour, cooled at room temperature and filtered. To the filtered solid was added 200 ml of acetic acid and 1 ml of concentrated hydrochloric acid, and the mixture was stirred for 5 hours. Cool, add 200 ml of methanol at room temperature, stir for 30 minutes, and filter. The filtrate solid was recrystallized from methanol to obtain 44.9 g (142 mmol) of the title compound as a solid (yield: 71%).

(B) Synthesis of 2-nitro-9,9'-spirobifluorene: (Compound 2)

The obtained Compound 1 (44.9 g) was dissolved in 250 ml of MC and then cooled to 10 ° C. The mixed acid prepared by mixing 20 g of HNO ₃ and ₉ g of H ₂ SO ₄ is gradually added dropwise over 1 hour, and the mixture is stirred at 10 to 15 ° C for 3 hours. Separation to remove the mixed acid layer and Na ₂ CO ₃ Is dissolved in 150 ml of water, and the mixture is stirred. Filter with Celite to remove impurities and separate layers. The MC layer is washed with MgSO ₄ and 10 g of neutral activated carbon is added. The mixture is stirred for 30 minutes and then filtered. Recrystallization from methanol gave a solid (40% yield, 79%) of the title compound (40.5 g, 112 mmol)

(C) Synthesis of 2-amino-9,9'-spirobifluorene: (Compound 3)

The obtained Compound 2 (40.5 g) was placed in a hydrogenation reactor, 500 ml of IPA was added, and the mixture was stirred with RPM 450. After confirming that the compound is completely dissolved, 1 g of Pd-C 10% (wet 50%) is added and H ₂ (g) is maintained at 3 atm for 1 hour. Filter to remove Pd-C. Concentrate IPA to the extent of about 100 ml, cool it to about 5 ℃ and filter. 100 ml of IPE was added and the mixture was refluxed for 1 hour, cooled at room temperature and filtered to obtain 33.8 g (102 mmol) of the title compound (yield: 91%).

(D) Synthesis of N-biphenyl-4-yl-spirobifluorene-2-amine: (Compound 4)

(33.8 g) obtained above, 15.8 g (68 mmol) of 4-bromobiphenyl and 200 ml of toluene were placed in a 500 ml three-necked flask and stirred for 1 hour. After stirring, add 8 g of t-BuONa (sodium tert butoxide) and stir for 30 minutes. After stirring, add ₂ g of Pd (dba) ₂ , stir for 30 minutes, add ₂ g of Tri (t-butyl) Phosphine and react at 60 ℃ for 6 hours. After filtration, 200 ml of water is added and the layers are separated. The toluene layer is washed with MgSO ₄ to remove water, and 5.8 g of neutral activated carbon is added. After stirring for 30 minutes, the filtrate is concentrated. And recrystallized from methanol to obtain 24.7 g (51 mmol) of the title compound (yield: 75%).

(E) N- biphenyl-4-yl -N- (4- (9- phenyl -9H- carbazol-3-yl) phenyl) RY lobby fluorene-2-amine Synthesis of (Compound 5)

20.2 g of the obtained compound 4 (24.7 g), 3- (4-bromophenyl) -9-phenyl-9H-carbazole and 350 ml of toluene were placed in a 500 ml three-necked flask and stirred for 1 hour. After stirring, add 6 g of sodium tert butoxide and stir for 30 minutes. After stirring, add ₂ g of Pd (dba) ₂ catalyst, stir for 30 minutes, add ₂ g of Tri (t-butyl) Phosphine and react at 80 ℃ for 8 hours. After the reaction, the reaction mixture is filtered and 300 ml of water is added thereto. The toluene layer is washed with MgSO ₄ , and 6.3 g of neutral activated carbon is added. The reaction mixture is stirred for 30 minutes and then filtered. And recrystallized from methanol to obtain 32.3 g (40 mmol) of the solid title compound (yield: 79%).

Example 2: Synthesis of N-biphenyl-4-yl-N- (4- (9- phenylcarbazol- 3-yl) -phenyl) -spiro (9H- fluorene-9,9- Synthesis: (Compound 10)

Synthesis was carried out according to Reaction Scheme 3 below.

[Reaction Scheme 3]

(A) Spiro (9H-fluorene-9,9'-9H-xanthene): (Compound 6)

39.2 g (200 mmol) of Xanthone and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in the step (A) of Example 1 to obtain 45.8 g (138 mmol) of the title compound as a solid (Yield: 69%).

(B) Spiro (2-nitro-9H-fluorene-9,9-9H-xanthene) (Compound 7)

The obtained compound 6 (45.8 g) was reacted in the same manner as in the step (B) of the above Example 1 to obtain 37.9 g (100 mmol) of the title compound (yield: 73%

(C) Synthesis of Spiro (2-amino-9H-fluorene-9,9-9H-xanthene) (Compound 8)

The obtained compound 7 (37.9 g) was reacted in the same manner as in the step (C) of Example 1 to obtain 39.7 g (86 mmol) of the title compound as a white solid (yield: 85%).

Synthesis of N-biphenyl-4-yl- spiro (9H- fluorene- 9,9- 9H -xanthene) -2- amine : (Compound 9)

The compound 8 (39.7 g) obtained above and 13.2 g (57 mmol) of 4-bromobiphenyl were reacted in the same manner as in the step (D) of Example 1 to obtain a solid (20.8 g, 41 mmol) of the title compound. (Yield: 73%)

Synthesis of N-biphenyl-4-yl-N- (4- (9- phenylcarbazol- 3-yl) -phenyl) -spiro (9H-fluorene- 9,9-9H-xanthene) : (Compound 10)

The obtained Compound 9 (20.8 g) and 3- (4-bromophenyl) -9-phenyl-9H-carbazole (16.3 g) were reacted in the same manner as in the step (E) of Example 1 to give the title compound (31 mmol) of a solid (yield: 75%).

Example 3: N- phenyl -N- (4- (9- phenyl-carbazol-3-yl) biphenyl) -4'-yl-spiro (9,10-dihydro-anthracene -10,10- dimethyl) - (9,9-9H-fluorene) -2'-amine: (Compound 15)

Synthesis was carried out according to Reaction Scheme 4 below.

[Reaction Scheme 4]

(A) Synthesis of spiro (9,10 -dihydro- 10,10-dimethylanthracene - 9,9-9H- fluorene ) (Compound 11)

44.4 g (200 mmol) of 9,10-dihydro-10,10-dimethyl anthracene and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in the step (A) of Example 1 to obtain the title compound 45.8 g (128 mmol) of a solid. (Yield: 64%).

(B) spiro-Synthesis of (9,10-dihydro-anthracene -10,10- dimethyl-2- nitro-fluoro -9,9-9H alkylene) (Compound 12)

The obtained compound 11 (45.8 g) was reacted in the same manner as in the step (B) of Example 1 to obtain 39.2 g (97 mmol) of the title compound (yield: 76%).

(C) spiro - Synthesis of (9,10-dihydro-anthracene -10,10- dimethyl -9,9-9H-2- fluoro-amino butylene) (Compound 13)

The obtained compound 12 (39.2 g) was reacted in the same manner as in the step (C) of Example 1 to obtain 32.3 g (87 mmol) of the title compound (yield: 89%).

(D) N- phenyl-spiro (9,10-dihydro-anthracene -10,10- dimethyl) - (fluoro 9,9-9H- alkylene) Synthesis of 2'-amine (Compound 14)

The obtained Compound 13 (32.3 g) and 8.9 g (57 mmol) of 4-bromobenzene were reacted in the same manner as in the step (D) of Example 1 to obtain 19.7 g (44 mmol) of the title compound as a solid. (Yield: 76%).

(E) N- phenyl -N- (4- (9- phenyl-carbazol-3-yl) biphenyl) -4'-yl-spiro (-10,10- dimethyl anthracene as 9,10-dihydroxy) - (9,9-9H-fluorene) -2'-amine: (Compound 15)

20.8 g of the obtained compound 14 (19.7 g) and 3- (4'-bromo-biphenyl) -4-yl-9-phenyl-9H- carbazole were reacted in the same manner as in step (E) To give 27.4 g (33 mmol) of the title compound as a white solid. (Yield: 74%).

Example 4: N- phenyl -N- (4- (9- phenyl-carbazol-3-yl) -biphenyl) -4'- yl-spiro (9H- fluorene flow -9,9-9H- thioxanthene ) -2-amine: (Compound 20)

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

[Reaction Scheme 5]

(A) Spiro (9H-fluorene-9,9'-9H-thioxanthine): (Compound 16)

42.4 g (200 mmol) of thioxanthone and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in the step (A) of Example 1 to obtain 48.7 g (140 mmol) of the title compound (Yield: 70%).

(B) Spiro (2-nitro-9H-fluorene-9,9'-9H-thioxanthine): (Compound 17)

The obtained Compound 16 (48.7 g) was reacted in the same manner as in the step (B) of Example 1 to obtain a solid (42.4 g, 107 mmol) of the title compound (yield: 77%).

(C) Synthesis of spiro (2-amino-9H-fluorene-9,9'-9H-thioxanthine) (Compound 18)

The obtained compound 17 (42.4 g) was reacted in the same manner as in the step (C) of Example 1 to obtain a solid (35.6 g, 91 mmol) of the title compound (yield: 84%).

(D) Synthesis of N-phenyl- spiro (9H- fluorene- 9,9-9H -thioxanthien ) -2- amine : (Compound 19)

The compound 18 (35.6 g) obtained above and 9.4 g (60 mmol) of 4-bromobenzene were reacted in the same manner as in the step (D) of Example 1 to obtain 19.6 g (45 mmol) of the title compound as a solid. (Yield: 74%).

(E) N- phenyl -N- (4- (9- phenyl-carbazol-3-yl) -biphenyl) -4'- yl-spiro (9H- fluorene flow-9,9-9H- thioxanthene) -2-amine: (Compound 20)

9.2 g of the obtained compound 19 (19.6 g) and 3- (4'-bromo-biphenyl) -4-yl-9-phenyl-9H- carbazole were reacted in the same manner as in the step (E) To obtain 28.6 g (34 mmol) of the title compound as a solid. (Yield: 77%).

Example 5: N-9,9- dimethyl-fluorene-2-yl -N- (4- (9- phenyl-carbazol-3-yl) phenyl)'s fatigue (10,11-dihydro -5H -Dibenzo [a, d] cycloheptene-5,9'-fluorene) -2'-amine: (Compound 25)

Synthesis was carried out according to Scheme 6 below.

[Reaction Scheme 6]

(A) Synthesis of spiro (10,11-dimethyl -5H- dibenzo [a, d] cycloheptene -5,9'- fluorene): (Compound 21)

52.8 g (200 mmol) of 10,11-dimethyl-dibenzosuberone and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in the step (A) of Example 1 to obtain the title compound 43.2 g (108 mmol) of a solid (yield: 54%).

(B) Synthesis of spiro (10,11-dimethyl -5H- dibenzo [a, d] cycloheptene-2-nitro-fluoro -5,9'- alkylene) (Compound 22)

The obtained compound 21 (43.2 g) was reacted in the same manner as in the step (B) of Example 1 to obtain 34.6 g (78 mmol) of the title compound (yield: 72%).

(C) spiro (10,11-dimethyl -5H- dibenzo [a, d] cycloheptene -5,9'- fluorene) Synthesis of 2'-amine (compound 23)

The obtained compound 22 (34.6 g) was reacted in the same manner as in the step (C) of Example 1 to obtain 27.8 g (67 mmol) of the title compound as a white solid (yield: 86%).

(D) N-9,9-dimethyl- fluoren -2-yl- spiro (10,11-dimethyl- 5H- dibenzo [a, d] cycloheptene- Synthesis of amine: (Compound 24)

The obtained compound 23 (27.8 g) and 2-bromo-9,9-dimethyl-9H-fluorene 12.3 g (45 mmol) were reacted in the same manner as in the step (D) of Example 1 to obtain the title compound 19.5 g (32 mmol) of a solid. (Yield: 72%).

(E) N-9,9- dimethyl-fluorene-2-yl -N- (4- (9- phenyl-carbazol-3-yl) phenyl) as a spigot (10,11-dimethyl-di -5H- Benzo [a, d] cycloheptene-5,9'-fluorene) -2'-amine: (Compound 25)

The compound 24 (19.5 g) obtained above and 12.7 g of 3- (4-bromophenyl) -9-phenyl-9H-carbazole were reacted in the same manner as in the step (E) of Example 1 to give 23.7 g (27 mmol) of a solid (yield: 80%).

Example 6: N-9,9- dimethyl-fluorene-2-yl -N- (4- (9- phenyl-carbazol-3-yl) phenyl)'s fatigue (5H- dibenzo [a, d ] Cycloheptene-5,9'-fluorene) -2'-amine: (Compound 30)

Synthesis was carried out according to Scheme 7 below.

[Reaction Scheme 7]

( A) Spiro (5H-dibenzo [a, d] cycloheptene-5,9'-fluorene) (Compound 26)

41.2 g (200 mmol) of 5H-dibenzo [a, d] cycloheptenone and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in the step (A) g (122 mmol) of a solid (yield: 61%).

(B) spiro synthesis of: Synthesis of (5H- dibenzo [a, d] cycloheptene-2-nitro -5,9'- fluorene): (Compound 27)

The obtained compound 26 (40.1 g) was reacted in the same manner as in the step (B) of Example 1 to obtain 35.9 g (93 mmol) of the title compound as a white solid (yield: 76%).

(C) spiro (5H- dibenzo [a, d] cycloheptene -5,9'- fluorene) Synthesis of 2'-amine (compound 28 screen)

The obtained compound 27 (35.9 g) was reacted in the same manner as in the step (C) of Example 1 to obtain 26.8 g (75 mmol) of the title compound (yield: 81%).

(D) N-9,9- dimethyl-fluorene-2-yl-spiro (5H- dibenzo [a, d] cycloheptene -5,9'- flat base fluorene) Synthesis of 2'-amine : (Compound 29)

The compound 28 (26.8 g) obtained above and 13.6 g (50 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene were reacted in the same manner as in the step (D) of Example 1 to obtain the title compound 19.0 g (35 mmol) of a solid (yield: 69%).

(E) N-9,9- dimethyl-fluorene-2-yl -N- (4- (9- phenyl-carbazol-3-yl) phenyl) as a spigot (5H- dibenzo [a, d] Cycloheptene-5,9'-fluorene) -2'-amine: (Compound 30)

The obtained compound 29 (19.0 g) and 3- (4-bromophenyl) -9-phenyl-9H-carbazole 13.9 g were reacted in the same manner as in the step (E) of Example 1 to give 21.2 g (26 mmol) of a solid (yield: 72%).

Example 7: N- phenyl -N- (7- (9- phenyl-carbazol-3-yl) 9,9-dimethyl -9H- fluorene) -2-yl-spiro (10-O-methyl -10H- 9,9-9H-fluorene) -2'-amine: (Compound 35)

Synthesis was carried out according to Scheme 8 below.

[Reaction Scheme 8]

(A) Spiro (10-methyl-10H-acridine-9,9-9H-fluorene) (Compound 31)

(200 mmol) of 2-bromobiphenyl and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in the step (A) of Example 1 to give 48.3 g (140 mmol) of the title compound. (Yield: 70%).

(B) Spiro (10- methyl- 10H-acridine-2-nitro-9,9-9H- fluorene ) (Compound 32)

The obtained Compound 31 (43.8 g) was reacted in the same manner as in the step (B) of Example 1 to obtain 42.0 g (108 mmol) of the title compound as a white solid. (Yield: 77%

(C) spiro (10-methyl-acridine -10H- -9,9-9H- fluorene) Synthesis of 2'-amine (compounds 33)

The obtained compound 32 (42.0 g) was reacted in the same manner as in the step (C) of Example 1 to obtain 34.5 g (96 mmol) of the title compound (yield: 89%).

(D) N- phenyl-spiro (10-methyl-acridine -10H- -9,9-9H- fluorene) Synthesis of 2'-amine (Compound 34)

The compound 33 (34.5 g) obtained above and 9.9 g (64 mmol) of 4-bromobenzene were reacted in the same manner as in the step (D) of Example 1 to obtain 18.7 g (43 mmol) of the title compound. (Yield: 67%).

(E) N- phenyl -N- (7- (9- phenyl-carbazol-3-yl) 9,9-dimethyl -9H- fluorene) -2-yl-in spigot (10-O-methyl -10H- 9,9-9H-fluorene) -2'-amine: (Compound 35)

22.0 g of the obtained compound 34 (18.7 g) and 3- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) (E), 28.3 g (33 mmol) of the title compound was obtained (yield: 76%).

Example 8: N- phenyl -N- (7- (9- phenyl-carbazol-3-yl) 9,9-dimethyl -9H- fluorene) -2-yl-spiro (anthracene-10-on--9 , 9-9H-fluorene) -2'-amine: (Compound 40)

Synthesis was carried out according to Scheme 9 below.

[Reaction Scheme 9]

(A) Synthesis of spiro (anthracene-10-one-9,9-9H-fluorene) (Compound 36)

41.6 g (200 mmol) of anthraquinone and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in the step (A) of Example 1 to obtain 44.0 g (128 mmol) of the title compound Yield: 64%)

(B) Spiro (9H-anthracene-10-one-2-nitro-9,9-9H- fluorene ) (Compound 37)

The obtained Compound 36 (44.0 g) was reacted in the same manner as in the step (B) of Example 1 to obtain 35.9 g (92 mmol) of the title compound as a white solid. (Yield: 72%

(C) Synthesis of spiro (anthracene-10-one-9,9-9H-fluorene) -2'-amine: (Compound 38)

The obtained compound 37 (35.9 g) was reacted in the same manner as in the step (C) of Example 1 to obtain a solid (26.5 g, 73 mmol) of the title compound (yield: 80%).

* (D), N- phenyl-spiro (anthracene-10-on--9,9-9H- fluorene) Synthesis of 2'-amine (compounds 39)

The compound 38 (26.5 g) obtained above and 7.6 g (49 mmol) of 4-bromobenzene were reacted in the same manner as in the step (D) of Example 1 to obtain the title compound (15.4 g, 35 mmol). (Yield: 72%).

(E) N- phenyl -N- (7- (9- phenyl-carbazol-3-yl) 9,9-dimethyl -9H- fluorene) -2-yl-in spigot (anthracene-10-on--9 , 9-9H-fluorene) -2'-amine: (Compound 40)

17.9 g of the obtained compound 39 (15.4 g) and 3- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) (E), 23.6 g (27 mmol) of the title compound was obtained (yield: 77%).

Claims (7)

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

(Wherein,
-Z- represents a single bond _{(-), -CR 5 R 6} -, -CR 5 R 6 -CR 5 R 6 -, -CR 5 = CR 6 -, -O-, -S-,> NR 5 or> C = O,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a C ₁ to C ₁₅ linear or branched alkyl group,
m, n, p, and q are independently the number of substituents of each benzene ring, 0, 1, 2, 3 or 4,
Ar ₁ and Ar ₂ are each independently a phenyl group which is unsubstituted or substituted with 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 by a C ₁ -C ₁₅ linear or branched alkyl group.)
The method according to claim 1,
A compound for producing an organic electroluminescence device, which is represented by the following formula (II).
[Formula II]

(Wherein,
-Z- represents a single bond _{(-), -CR 5 R 6} -, -CR 5 R 6 -CR 5 R 6 -, -CR 5 = CR 6 -, -O-, -S-,> NR 5 or> C = O,
The dotted line is absent or -CR < ₁₀ > R < ₁₁ &
Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is independently a hydrogen atom or a C ₁ to C ₁₅ linear or branched Alkyl group,
m, n, p, q, s, and t are independently 0, 1, 2, 3 or 4 and r is 0, 1, 2, 3, 4 or 5,
The method according to claim 1,
A compound for the production of an organic electroluminescence device, which is represented by the following formula (III).
[Formula (III)

(Wherein,
-Z- represents a single bond _{(-), -CR 5 R 6} -, -CR 5 R 6 -CR 5 R 6 -, -CR 5 = CR 6 -, -O-, -S-,> NR 5 or> C = O,
The dotted line is absent or -CR < ₁₀ > R < ₁₁ &
Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is independently a hydrogen atom or a C ₁ to C ₁₅ linear or branched Alkyl group,
m, n, p, q, s, and t are independently 0, 1, 2, 3 or 4 and r is 0, 1, 2, 3, 4 or 5,
The method according to claim 2 or 3,
Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen atom, a methyl group or an ethyl group, compound.
The method according to claim 1,
Wherein the compound is selected from the group consisting of the following chemical formulas.

(In the above equations,
And, - the dotted line is not present or -C (CH _{3) 2}
R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a methyl group or an ethyl group,
and r is 0, 1, 2, 3, 4 or 5 as the substitution number of each benzene ring.
An organic electroluminescent device comprising the compound according to any one of claims 1 to 5 in a hole transport layer.
An organic electroluminescent device comprising a compound according to any one of claims 1 to 5 in a light emitting layer.

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