KR20130140303A - Novel compounds for organic electroluminescent device - Google Patents

Abstract

The present invention relates to a compound for manufacturing an organic electroluminescent device represented by chemical formula I. In chemical formula I, R1 to R6 are alkyl groups of C1-C5 with hydrogen atoms, Ar1 and Ar2 are unsubstituted phenyl groups or phenyl groups substituted with C1-C15 alkyl groups, unsubstituted biphenyl groups or phenyl groups substituted with C1-C15 alkyl groups, or unsubstituted fluorene groups or phenyl groups substituted with C1-C15 alkyl groups.

Description

Novel compounds for organic electroluminescent device

The present invention relates to a compound used in the manufacture of an organic electroluminescent device, and more particularly to a novel organic compound that can be usefully used as a hole transport material.

An organic electroluminescent device refers to a self-luminous organic material that emits light when a current flows through a fluorescent organic compound, and is also referred to as organic light emitting diodes (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 materials used in OLEDs should have a suitable molecular weight to enable vacuum deposition, high thermal stability at glass transition temperature (Tg) and pyrolysis temperature (Td), and Joule heat generated during device operation. It must be amorphous so that the device is not destroyed by the resulting crystallization and the adhesion to adjacent layers is good while not being transferred to other layers.

The material used for the hole transport layer (HTL) not only transports the holes flowing from the hole injection layer to the light emitting layer quickly but also increases the probability of exciton formation by binding electrons in the light emitting layer. In order to suppress hole excitation at the hole transport layer and the light emitting layer interface, the hole transport material should have a high ionization level between the hole injection layer and the light emitting layer, and have a large band gap. 2). In addition, the mechanical properties such as heat resistance, durability and the ability to control the electrons from moving from the light emitting layer to the hole transport layer is required.

The characteristics of the hole transport material are summarized as follows.

High hole mobility

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 bandgap energy

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

The triphenylamine structure is known to have excellent hole mobility, and many diamine, triamine and tetratriamine derivatives based on the triphenylamine structure have been developed as hole transport materials. Initially, TPD (Triphenyldiamine) was used, but the glass transition temperature, one of the most important characteristics, was low at 60 ℃, which was vulnerable in terms of thermal stability. In order to improve the thermal stability, derivatives having increased molecular units of triphenylamine backbones or expanded molecular weight such as α-NPD and spiro-TTB have been mainly developed.

Representative hole transport materials developed are shown below.

As mentioned above, for long life and high power efficiency of OLED display, hole transport material should have high hole mobility, thermal stability and band gap energy, and should have energy level, low LUMO value, and amorphousness between hole injection layer and light emitting layer. In addition, the development of new materials to meet these properties more is required.

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

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

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

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

[Formula 1]

(Wherein,

-Z- is 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 straight or branched alkyl group,

m, n, p, q are the number of substitution of each benzene ring, each independently 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 straight 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 to C ₁₅ straight or branched alkyl group.)

The compound of formula I may preferably be used as a hole transport material.

The novel organic compound according to the present invention has high hole mobility, thermal stability, high bandgap energy, energy level between the hole injection layer and the light emitting layer, low LUMO value, amorphousness, etc., and thus can be usefully used for hole transport materials. .

Therefore, the OLED display using the compound of the present invention has the effect of high power efficiency and 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.
Figure 3 shows the chemical formula of the compound for an organic electroluminescent 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 aryl amine derivative in which the spiro polycyclic structure compound and the 9-phenylcarbazole derivative are amine-bonded can be usefully used as an organic electroluminescent device, especially a major transport material.

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

(I)

(Wherein,

-Z- is 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 straight or branched alkyl group,

m, n, p, q are the number of substitution of each benzene ring, each independently 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 straight 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 to C ₁₅ straight or branched alkyl group.)

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

In the present invention, the spirofluorene derivative is characterized in that the benzene rings opposed to the fluorine ring cyclized to improve the bond stability between the benzene ring, the cyclization is a single bond (direct bond between benzene) or C ₁ It is characterized by being bonded to an alkyl, alkene or ketone group of ˜C ₂ , or bonded to O, S, N atoms. The cyclization improves the hole transporting capacity, heat resistance, and durability of the compound without affecting conjugated double bonds.

The spirofluorene derivatives include spirobifluorene, spiro (fluorene-xanthene), spiro (fluorene-9,10-dihydro-10,10-dialkylanthracene), spiro (fluorene-thioxanthene) , Spiro (fluorene-10,11-dihydro-5H-dibenzo [a, d] cycloheptene), spiro (fluoroene-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 in the benzene ring are a hydrogen atom or a C ₁ to C ₁₅ straight or branched alkyl group. Since the substituent does not affect the conjugated double bond, there is no significant difference in the basic skeleton structure and the hole transport capacity. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl groups by vacuum deposition of amine derivatives. In view of molding stability, it is preferably an alkyl group of C ₁ to C ₆ , more preferably an unsubstituted (hydrogen atom) or a methyl group (C ₁ ).

In consideration of the bandgap energy, the energy level, and the LUMO value, the sum of the benzene rings of Ar ₁ and Ar ₂ in Chemical Formula I is preferably 3. That is, when Ar ₁ is a biphenyl group or a derivative thereof, as shown in formula (II), Ar ₂ is preferably a phenyl group, and when Ar ₁ is a phenyl group, as shown in formula (III), Ar ₂ is a biphenyl group or derivative thereof Is preferably.

[Formula II]

[Formula (III)

(Wherein,

-Z- is 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- ,

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 or a straight or branched chain of C ₁ to C ₁₅ An alkyl group,

m, n, p, q, s, t are the number of substitution of each benzene ring, each 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 scheme I illustrates a preferred synthesis method, may be prepared by a combination of other known synthesis methods, the order of the amine reaction is not limited.

[Reaction Scheme 1]

2-bromobiphenyl was prepared using Mg powder to prepare Grignard reagent, followed by reaction with dibenzo cycloketone compound (compound a), and then under acid conditions, or under n-BuLi (butyllithium) conditions. The reaction is carried out under acid conditions to synthesize spirofluorene derivative (Compound b).

The spirofluorene derivative (compound b) prepared above is reacted with a mixture of nitric acid or nitric acid / sulfuric acid to synthesize an amino compound (compound c), and then hydrogenated under high pressure to synthesize a primary amine compound (compound d).

The primary amine compound (compound d) prepared above is amine reacted with Ar ₁ -Br (compound e) to synthesize a secondary amine compound (compound f). In this case, in order to prevent two Ar ₁ bonds to the primary amine, the compound d is preferably used in an amount of 1.3 equivalent or more based on Ar ₁ -Br.

The target compound (compound h) is synthesized by amine reaction of the prepared secondary amine compound (compound f) with the phenylcarbazole derivative compound (compound g).

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- Carbazole -3 days)- Phenyl ) - Spirobifluorene -2- Min Synthesis of: (Compound 5)

Synthesis was carried out according to Reaction Scheme 2 below.

[Reaction Scheme 2]

(A) 9,9'- Spirobifluorene  Synthesis: (Compound 1)

46.4 g (200 mmol) of 2-bromobiphenyl, 5.3 g of magnesium turning and 900 ml of dry THF are placed in a three neck flask and refluxed for 4 hours. 36.0 g (200 mmol) of fluorenone is dissolved in 300 ml of dry THF and slowly added dropwise to reflux for 2 hours. After cooling to about 10 ℃ 1N HCl 200ml was added and stirred for 30 minutes, THF was concentrated, 1000ml of water was added and stirred and filtered. The filtered solid was dissolved in toluene to remove water remaining as MgSO ₄ , 7.0 g of neutral activated carbon was added thereto, stirred for 30 minutes, and concentrated by filtration. 400 ml of cyclohexane was added to the concentrated residue, followed by stirring for 1 hour, followed by cooling to room temperature. 200 ml of acetic acid and 1 ml of concentrated hydrochloric acid were added to the filtered solid, and the mixture was stirred for 5 hours. After cooling, 200 ml of methanol was added at room temperature, and the mixture was stirred for 30 minutes and then filtered. The filtered solid was recrystallized in methanol to give 44.9 g (142 mmol) of the title compound (yield 71%).

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

Compound 1 (44.9 g) obtained above was dissolved in 250 ml of MC, and then cooled to 10 ° C. 20g HNO ₃ and H ₂ SO ₄ The mixed acid produced by mixing 9 g was slowly added dropwise over 1 hour, and then stirred for 3 hours while maintaining 10 to 15 ° C. Layer separated to remove mixed acid and Na ₂ CO ₃ 8.5g is dissolved in 150ml of water and stirred. Filter with Celite to remove impurities and separate layers. Water was removed from the MC layer using MgSO ₄ , 10 g of neutral activated carbon was added thereto, stirred for 30 minutes, and then filtered and concentrated. Recrystallization with methanol gave 40.5 g (112 mmol) of the title compound as a solid (yield 79%).

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

Compound 2 (40.5 g) obtained above was added to a hydrogen reactor, 500 ml of IPA was added thereto, and the mixture was stirred at RPM 450. After heating to 60 ° C. to confirm that the compound is completely dissolved, 1 g of Pd-C 10% (wet 50%) is added thereto, and H ₂ (g) is reacted for 1 hour while maintaining 3 atm. Filtration removes Pd-C. Concentrate until 100 ml of IPA remains and cool by 5 ℃. 100 ml of IPE was added thereto, refluxed for 1 hour, and the mixture was cooled to room temperature and filtered to obtain 33.8 g (102 mmol) of the title compound (yield 91%).

(D) N-biphenyl-4-yl- Spirobifluorene -2- Amine  Synthesis: (Compound 4)

Compound 3 (33.8 g), 4-bromobiphenyl 15.8 g (68 mmol) and 200 ml of toluene were added to 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, ₂ g of Pd (dba) ₂ was added, and after stirring for 30 minutes, ₂ g of Tri (t-butyl) Phosphine was added and reacted at 60 ° C. for 6 hours. After the reaction, the mixture was filtered, 200 ml of water was added thereto, and the layers were separated. The water was removed from the toluene layer using MgSO ₄ , 5.8 g of neutral activated carbon was added thereto, stirred for 30 minutes, and then filtered and concentrated. Recrystallization with methanol gave 24.7 g (51 mmol) of the title compound as a solid (yield 75%).

(E) N-biphenyl-4-yl-N- (4- (9- Phenyl -9H- Carbazole -3 days)- Phenyl ) - Spirobifluorene -2- Min Synthesis of: (Compound 5)

Compound 4 (24.7 g) and 20.2 g of 3- (4-bromophenyl) -9-phenyl-9H-carbazole and 350 ml of toluene were added to 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, ₂ g of Pd (dba) ₂ catalyst was added, and after stirring for 30 minutes, ₂ g of Tri (t-butyl) Phosphine was added and reacted at 80 ° C for 8 hours. After the reaction, the mixture was filtered, 300 ml of water was added, and the layers were separated. The water was removed from the toluene layer using MgSO ₄ , 6.3 g of neutral activated carbon was added thereto, stirred for 30 minutes, and then filtered and concentrated. Recrystallization with methanol gave 32.3 g (40 mmol) of the title compound as a solid (yield 79%).

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

Synthesis was carried out according to Reaction Scheme 3 below.

Scheme 3

(A) Of spiro (9H-fluorene-9,9'-9H-xanthene)  Synthesis: (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 step (A) of Example 1 to obtain 45.8 g (138 mmol) of the title compound. (Yield 69%)

(B) Spiro (2-nitro-9H- Fluorene -9,9-9H- Xanthene ) Synthesis: (Compound 7)

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

(C) Spiro (2-amino-9H- Fluorene -9,9-9H- Xanthene ) Synthesis: (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 (yield: 85%).

(D) N-biphenyl-4-yl- Spiro (9H- Fluorene -9,9-9H- Xanthene )-2- Amine  Synthesis: (Compound 9)

Compound 8 (39.7 g) and 13.2 g (57 mmol) of 4-bromobiphenyl were reacted in the same manner as in Example (D), to obtain 20.8 g (41 mmol) of the title compound. (Yield 73%)

(E) N-biphenyl-4-yl-N- (4- (9- Phenylcarbazole -3-yl) -phenyl) -spiro (9H- Fluorene Synthesis of -9,9-9H-Xanthene): (Compound 10)

The obtained compound 9 (20.8 g) and 16.3 g of 3- (4-bromophenyl) -9-phenyl-9H-carbazole were reacted in the same manner as in step (E) of Example 1, to give 25.5 g of the title compound. (31 mmol) of a solid was obtained. (Yield: 75%)

Example  3: N-phenyl-N- (4- (9-phenylcarbazol-3-yl) -biphenyl) -4'-yl-spiro (9,10-dihydro-10,10- Dimethyl anthracene )-(9,9-9H- Fluorene )-2'- Amine  Synthesis of Synthesis: (Compound 15)

Synthesis was carried out according to Reaction Scheme 4 below.

[Reaction Scheme 4]

(A) Spiro (9,10- Dihydro -10,10- Dimethyl anthracene -9,9-9H- Fluorene ) Synthesis: (Compound 11)

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

(B) Spiro (9,10- Dihydro -10,10- Dimethyl anthracene -9,9-9H-2-nitro- Fluorene ) Synthesis: (Compound 12)

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

(C) Spiro (9,10- Dihydro -10,10- Dimethyl anthracene -9,9-9H-2-amino- Fluorene ) Synthesis: (Compound 13)

Compound 12 (39.2 g) obtained above 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 -10,10- Dimethyl anthracene )-(9,9-9H- Fluorene )-2'- Amine  Synthesis: (Compound 14)

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

(E) N- Phenyl -N- (4- (9- Phenylcarbazole -3-yl) -biphenyl) -4'-yl-spiro (9,10- Dehydro Rho-10,10- Dimethyl anthracene )-(9,9-9H- Fluorene )-2'- Amine  Synthesis: (Compound 15)

Compound 14 (19.7 g) and 2-0.8 g of 3- (4'-bromo-biphenyl) -4-yl-9-phenyl-9H-carbazole were obtained in the same manner as in step (E) of Example 1. Reaction to give 27.4 g (33 mmol) of the title compound (yield: 74%).

Example  4: N-phenyl-N- (4- (9-phenylcarbazol-3-yl) -biphenyl) -4'-yl-spiro (9H-fluoroene-9,9-9H-thioxanthene)- 2- Amine  Synthesis: (Compound 20)

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

[Reaction Scheme 5]

(A) Of spiro (9H-fluorene-9,9'-9H-thioxanthene)  Synthesis: (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 step (A) of Example 1 to obtain 48.7 g (140 mmol) of the title compound as a solid. (Yield 70%)

(B) Spiro (2-nitro-9H- Fluorene -9,9'-9H- Thioxanthene ) Synthesis: (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 42.4 g (107 mmol) of the title compound (yield: 77%).

(C) Spiro (2-amino-9H- Fluorene -9,9'-9H- Thioxanthene ) Synthesis: (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 35.6 g (91 mmol) of the title compound (yield: 84%).

(D) N- Phenyl - Spiro (9H- Fluorene -9,9-9H- Thioxanthene )-2- Amine  Synthesis: (Compound 19)

Compound 18 (35.6 g) obtained above was reacted with 9.4 g (60 mmol) of 4-bromobenzene in the same manner as in Example (D), to obtain 19.6 g (45 mmol) of the title compound. (Yield 74%)

(E) N- Phenyl -N- (4- (9- Phenylcarbazole -3-yl) -biphenyl) -4'- yl Spiro (9H- Fluorene -9,9-9H-thioxanthene) -2- Amine  Synthesis: (Compound 20)

Compound 19 (19.6 g) and 21.2 g of 3- (4'-bromo-biphenyl) -4-yl-9-phenyl-9H-carbazole were obtained in the same manner as in step (E) of Example 1. Reaction to give 28.6 g (34 mmol) of the title compound (yield: 77%).

Example  5: N-9,9-dimethyl- Fluorene 2-yl-N- (4- (9- Phenylcarbazole -3 days)- Phenyl )-Spiro (10,11- Dihydro -5H- Dibenzo [a, d] cycloheptene -5,9'- Fluorene )-2'- Amine  Synthesis: (Compound 25)

Synthesis was carried out according to Scheme 6 below.

[Reaction Scheme 6]

(A) Spiro (10,11-dimethyl-5H- Dibenzo [a, d] cycloheptene -5,9'- Fluorene ) Synthesis: (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 step (A) of Example 1 to give the title compound 43.2 g (108 mmol) of solid was obtained. (Yield: 54%)

(B) Spiro (10,11-dimethyl-5H- Dibenzo [a, d] cycloheptene -2-nitro-5,9'- Fluorene ) Synthesis: (Compound 22)

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

(C) Spiro (10,11-dimethyl-5H- Dibenzo [a, d] cycloheptene -5,9'- Fluorene )-2'- Amine Synthesis of: (Compound 23)

Compound 22 (34.6 g) obtained above 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 (yield: 86%).

(D) N-9,9-dimethyl- Fluorene 2-yl-spiro (10,11-dimethyl-5H- Dibenzo [a, d] cycloheptene -5,9'- Fluorene )-2'- Amine  Synthesis: (Compound 24)

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

(E) N-9,9-dimethyl- Fluorene 2-yl-N- (4- (9- Phenylcarbazole -3 days)- Phenyl ) -Spiro (10,11-dimethyl-5H- Dibenzo [a, d] cycloheptene -5,9'- Fluorene )-2'- Amine  Synthesis: (Compound 25)

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

Example  6: N-9,9-dimethyl- Fluorene 2-yl-N- (4- (9- Phenylcarbazole -3 days)- Phenyl )-Spiro (5H- Dibenzo [a, d] cycloheptene -5,9'- Fluorene )-2'- Amine  Synthesis: (Compound 30)

Synthesis was carried out according to Scheme 7 below.

[Reaction Scheme 7]

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

41.2 g (200 mmol) of 5H-dibenzo [a, d] cycloheptene-one and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in step (A) of Example 1 to obtain the title compound 40.1. g (122 mmol) of solid was obtained. (Yield: 61%)

(B) Spiro (5H- Dibenzo [a, d] cycloheptene -2-nitro-5,9'- Fluorene Synthesis of): (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 (yield: 76%).

(C) Spiro (5H- Dibenzo [a, d] cycloheptene -5,9'- Fluorene )-2'- Amine  Synthesis: (Compound 28)

Compound 27 (35.9 g) obtained above was reacted in the same manner as in 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'- Fluorene )-2'- Amine  Synthesis of Synthesis: (Compound 29)

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

(E) N-9,9-dimethyl- Fluorene 2-yl-N- (4- (9- Phenylcarbazole -3 days)- Phenyl )-Spiro (5H- Dibenzo [a, d] cycloheptene -5,9'- Fluorene )-2'- Amine  Synthesis: (Compound 30)

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

Example  7: N- Phenyl -N- (7- (9- Phenylcarbazole -3-yl) -9,9-dimethyl-9H- Fluorene ) -2-yl-spiro (10-methyl-10H- Acridine -9,9-9H- Fluorene )-2'- Amine  Synthesis: (Compound 35)

Synthesis was performed according to Scheme 8 below.

[Reaction Scheme 8]

(A) Spiro (10- methyl -10H- Acridine -9,9-9H- Fluorene ) Synthesis: (Compound 31)

41.8 g (200 mmol) of 10-methylacridin-9-10H-one and 46.4 g (200 mmol) of 2-bromobiphenyl were reacted in the same manner as in step (A) of Example 1 to give 48.3 g of the title compound. (140 mmol) of a solid was obtained. (Yield: 70%)

(B) Spiro (10- methyl -10H- Acridine 2-nitro-9,9-9H- Fluorene ) Synthesis: (Compound 32)

Compound 31 (43.8 g) obtained above was reacted in the same manner as in step (B) of Example 1, to obtain 42.0 g (108 mmol) of the title compound (yield: 77%).

(C) Spiro (10- methyl -10H- Acridine -9,9-9H- Fluorene )-2'- Amine  Synthesis: (Compound 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 -10H- Acridine -9,9-9H- Fluorene )-2'- Amine  Synthesis: (Compound 34)

Compound 33 (34.5 g) and 9.9 g (64 mmol) of 4-bromobenzene were reacted in the same manner as in (D) of Example 1, to obtain a solid of 18.7 g (43 mmol) of the title compound. (Yield 67%)

(E) N- Phenyl -N- (7- (9- Phenylcarbazole -3-yl) -9,9-dimethyl-9H- Fluorene ) -2-yl-spiro (10- methyl -10H- Acridine -9,9-9H- Fluorene )-2'- Amine  Synthesis: (Compound 35)

The obtained compound 34 (18.7 g) and 2-2.0 g of 3- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole were prepared in Example 1. The reaction was carried out in the same manner as in (E), to obtain 28.3 g (33 mmol) of the title compound (yield: 76%).

Example  8: N-phenyl-N- (7- (9-phenylcarbazol-3-yl) -9,9-dimethyl-9H-fluorene) -2-yl-spiro (anthracene-10-one-9,9 -9H- Fluorene )-2'- Amine  Synthesis: (Compound 40)

Synthesis was performed according to Scheme 9 below.

[Reaction Scheme 9]

(A) Of spiro (anthracene-10-one-9,9-9H-fluorene)  Synthesis: (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 step (A) of Example 1, to obtain 44.0 g (128 mmol) of the title compound. Yield: 64%)

(B) Spiro (9H-anthracene-10-on-2-nitro-9,9-9H- Fluorene ) Synthesis: (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 (yield: 72%).

(C) Spiro (Anthracene-10-one-9,9-9H- Fluorene )-2'- Amine  Synthesis: (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 26.5 g (73 mmol) of the title compound (yield: 80%).

(D) N- Phenyl - Spiro (Anthracene-10-one-9,9-9H- Fluorene )-2'- Amine  Synthesis: (Compound 39)

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

(E) N- Phenyl -N- (7- (9- Phenylcarbazole -3-yl) -9,9-dimethyl-9H- Fluorene ) -2-yl-spiro (anthracene-10-one-9,9-9H- Fluorene )-2'- Amine  Synthesis: (Compound 40)

The obtained compound 39 (15.4 g) and 17.9 g of 3- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole were prepared in Example 1 The reaction was carried out in the same manner as in (E), to obtain 23.6 g (27 mmol) of the title compound (yield: 77%).

Claims (7)

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

(Wherein,
-Z- is 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 straight or branched alkyl group,
m, n, p, q are the number of substitution of each benzene ring, each independently 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 straight 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 to C ₁₅ straight or branched alkyl group.)
The method of claim 1,
The compound for producing an organic electroluminescent device represented by the formula (II).
[Formula II]

(Wherein,
-Z- is 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- ,
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 or a straight or branched chain of C ₁ to C ₁₅ An alkyl group,
m, n, p, q, s, t are the number of substitution of each benzene ring, each independently 0, 1, 2, 3 or 4, and r is 0, 1, 2, 3, 4 or 5.
The method of claim 1,
The compound for producing an organic electroluminescent device represented by the formula (III).
[Formula (III)

(Wherein,
-Z- is 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- ,
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 or a straight or branched chain of C ₁ to C ₁₅ An alkyl group,
m, n, p, q, s, t are the number of substitution of each benzene ring, each 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,
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 organic electroluminescent device for manufacturing an ethyl group compound.
The method of claim 1,
The compound is an organic electroluminescent device manufacturing compound which is selected from the group consisting of the following formula.

(In the above formulas,
The dashed line is absent or -C (CH ₃ ) _2- ,
R ₅ and R ₆ And R ₇ are each independently a hydrogen atom, a methyl group or an ethyl group,
r is 0, 1, 2, 3, 4 or 5 as the number of substitution 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 the compound according to any one of claims 1 to 5 in a light emitting layer.

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