WO2012043996A2

WO2012043996A2 - Compound in which amine derivative is substituted with fluorene, organic electronic device using same, and terminal thereof

Info

Publication number: WO2012043996A2
Application number: PCT/KR2011/006749
Authority: WO
Inventors: 김동하; 문성윤; 박정철; 주진욱; 백장열; 김원삼; 박성진; 김은경; 최대혁; 박정환; 홍철광; 유한성
Original assignee: 덕산하이메탈(주)
Priority date: 2010-09-30
Filing date: 2011-09-09
Publication date: 2012-04-05
Also published as: WO2012043996A3

Abstract

The present invention provides a compound in which an amine derivative is substituted with a fluorene, an organic electronic device using the same, and a terminal thereof.

Description

A compound in which an amine derivative is substituted for fluorene, an organic electric device using the same, and a terminal thereof

The present invention relates to a compound in which an amine derivative is substituted for fluorene, an organic electric device using the same, and a terminal thereof.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. The principle is that when a small amount of a dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

Embodiments of the present invention to solve the problems of the above-described background, it was found that a compound in which amine derivative is substituted in fluorene, and when the compound is applied to an organic electronic device, the efficiency of the device, the driving voltage drop, It has been found that it can have an increase in life and stability.

Accordingly, an object of the present invention is to provide a compound in which an amine derivative is substituted for fluorene, and an organic electric device using the same, an electronic device, or a terminal thereof.

In one aspect, the present invention provides a compound of the formula:

The present invention is a compound in which an amine derivative is substituted for fluorene, and may be used as a hole injection, hole transport, electron injection, electron transport, light emitting material, and passivation material in organic electronic devices, and in particular, a light emitting material and a host / It can be used as a host or dopant in a dopant, and can be used as a hole injection and hole transport layer.

The present invention also provides an organic electronic device using the compound having the above formula, and an electronic device or terminal including the organic electronic device.

When the compound is applied to an organic electronic device and an electronic device or a terminal including the organic electronic device, the efficiency of the device may be increased, the driving voltage may be decreased, the lifetime may be increased, and the stability may be increased.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

The present invention provides a compound of Formula 1 below.

[Formula 1]

In Chemical Formula 1, the Cz group may be a substituted or unsubstituted carbazole derivative which may be represented by the following Chemical Formula 2, but is not limited thereto.

[Formula 2]

In this case, R ₃ -R ₇ which may be substituted on the carbon atom of carbazole in Formula 2 may be the same or different from each other independently, hydrogen atom, deuterium, tritium; Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, S, N, O, P and Si Substituted or unsubstituted hetero aryl group having 5 to 60 carbon atoms, substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylcycle having 5 to 60 carbon atoms Amino, substituted or unsubstituted alkoxycarbonyl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups or carboxyl groups It may be selected from the group consisting of groups, etc., but is not limited thereto. In addition, R <_3> -R <_7> may combine with adjacent groups, and may form the ring (ring).

On the other hand, X may be the same as R ₃ -R ₇ but is not limited thereto. m may be an integer of 1 to 3, but is not limited thereto.

In addition, in Formula 1, Ar ₁ to Ar ₃ may be the same as or different from each other, and each independently substituted or unsubstituted aryl group having 3 to 60 nuclear atoms, or at least one of S, N, O, P, and Si. Substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, including a hetero atom of, may be a substituted or unsubstituted alkyl group, but is not limited thereto. At this time, Ar ₁ ~ Ar ₃ may be bonded to each other adjacent groups to form a ring (ring). Meanwhile, Ar ₁ to Ar ₃ are specifically substituted or unsubstituted phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, fluorene group, thiophene group, pyrrole group, furan group, pyridyl group in the group consisting of May be selected but is not limited thereto.

Meanwhile, in Formula 1, R ₁ and R ₂ , R ′, and R ″ may be the same as or different from each other, and each independently hydrogen atom, deuterium, tritium; Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, S, N, O, P and Si Substituted or unsubstituted hetero aryl group having 5 to 60 carbon atoms, substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms Amino, substituted or unsubstituted alkoxycarbonyl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups or carboxyl groups It may be selected from the group consisting of, but not limited thereto. In addition, R ₁ and R ₂ , R ', and R''may combine with each other to form a ring.

Substituents of X, R ₃ -R _7, R ₁ and R ₂ , R ', and R''in Formula 1 may be substituted or unsubstituted, and when substituted, hydrogen atom, deuterium, tritium; Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, S, N, O, P and Si Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one hetero atom, substituted or unsubstituted A substituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted nuclear C5-C60 aryloxy group, a substituted or unsubstituted C5-C60 aryl cy Amino, substituted or unsubstituted alkoxycarbonyl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups or carboxyl groups It may be substituted with one selected from the group consisting of groups and the like.

Compounds represented by Formula 1 may be one of the compounds represented by Formula 3 below, but is not limited thereto. At this time, the compounds represented by the formula (1) is substituted with the substituted or unsubstituted substituents of X, R ₃ -R _7, R ₁ and R ₂ , R 'and R''of the formula 1 It is practically difficult to exemplify all compounds in a broad relationship Therefore, exemplary compounds are exemplarily described, but the compounds represented by Formula 1, which are not described in Formula 3, may also form part of the present specification.

[Formula 3]

In addition, the substituents in Chemical Formulas 1 to 3 may be substituted or unsubstituted again even if not mentioned above, and the substituents may be substituted again.

Various organic electric devices exist in which compounds in which an amine derivative is substituted for fluorene described with reference to Chemical Formulas 1 to 3 are used as the organic material layer. Examples of organic electroluminescent devices in which compounds substituted with an amine derivative in fluorene described with reference to Chemical Formulas 1 to 3 may be used include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor. And the like (organic TFT).

An organic electroluminescent device (OLED) is described as an example of an organic electroluminescent device to which compounds in which an amine derivative is substituted in fluorene described with reference to Chemical Formulas 1 to 3 can be applied, but the present invention is not limited thereto. Compounds in which an amine derivative is substituted for fluorene described above may be applied.

Another embodiment of the present invention is an organic electric device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer of the organic electric field comprising the compounds of Formulas 1 to 3 Provided is a light emitting device.

For example, an organic electric device including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers is represented by Chemical Formulas 1 to 3 Provided are an organic light emitting display device including a compound in which an amine is substituted for fluorene.

The organic material layer includes a hole injection layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, wherein one of the layers is an amine substituted with fluorene represented by the formula (1) It may include.

In another aspect, the organic material layer includes at least one layer of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein one of the layers is fluorene represented by Formulas 1 to 3 It may also include a compound substituted with an amine.

Specifically, the organic material layer may include a light emitting layer, and the light emitting layer may include a compound in which an amine is substituted for fluorene represented by Chemical Formulas 1 to 3.

In addition, the organic material layer may include an electron transport layer, and the electron transport layer may include a compound in which an amine is substituted with fluorene represented by Chemical Formulas 1 to 3.

In addition, the organic material layer may include a light emitting auxiliary layer, and the light emitting auxiliary layer may include a compound in which an amine is substituted for fluorene represented by Chemical Formulas 1 to 3.

In an organic light emitting display device according to another embodiment of the present invention, at least one layer of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is formed to include the compounds of Formulas 1 to 3 above. Except for the above, it may be manufactured in a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of the organic light emitting display device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode. Although not shown, the organic light emitting diode may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for preventing the movement of electrons, and a protective layer. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound in which the amine derivative is substituted for fluorene described with reference to Chemical Formulas 1 to 3 may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer. Specifically, the compound in which the amine derivative is substituted for fluorene described with reference to Chemical Formulas 1 to 3 may include at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, and a protective layer. It may be used in place of or in combination with them. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, the compound may be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a light emitting material and a passivation (kepping) material according to the compound in which the amine derivative is substituted for fluorene described with reference to Chemical Formulas 1 to 3, In particular, it can be used alone as a light emitting material and a host or dopant.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.

In addition, the organic material layer may be formed by using a variety of polymer materials, and by using a process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.

The organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process in which the amine derivative is substituted with fluorene as described above. .

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

The hole injection material is a material capable of well injecting holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene and silicon germanium oxide. Compound, a silicon-based arylamine compound, and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency. [(1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used. When the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene. Can be used for

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.

The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

As described above, hole injection materials, hole transport materials, and luminescent materials suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, and white, depending on the compound in which the amine derivative is substituted for fluorene described with reference to Chemical Formulas 1 to 3 It can be used as an electron transport material and an electron injection material, and can be used as a host or dopant material of various colors.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.

실시예Example

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Preparation Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

제조예 1Preparation Example 1

Hereinafter, the preparation or synthesis examples of the compounds in which the amine derivative is substituted for fluorene belonging to Chemical Formulas 1 to 3 will be described. However, one or two of the compounds in which the amine derivative is substituted for the fluorene belonging to the general formula (1) to the fluorene belonging to the general formula (1) to 3 because of the large number of compounds substituted by the exemplified by one or two. Those skilled in the art, that is, those skilled in the art can prepare a compound in which an amine derivative is substituted for fluorene belonging to the present invention which is not illustrated by the preparation examples described below.

In other words, as can be seen through Scheme 1, the intermediate 4 and the intermediate 2 may be reacted to finally synthesize the compounds represented by Chemical Formulas 1 to 3. In this case, intermediate 4 may be synthesized through compound 3 in Scheme 1, and intermediate 2 may be synthesized through compounds 1 and 2. Detailed description thereof will be described below in detail.

Scheme 1

[Revision under Rule 91 09.11.2011]

중간체 4의 합성Synthesis of Intermediate 4

4a-1(9-Phenylcarbazole)의 합성 Synthesis of 4a-1 (9-Phenylcarbazole)

Scheme 2

9-phenyl carbazole (20 g, 82.2 mmol), NBS (15.36 g, 86.31 mmol) and methylene chloride (200 mL) were added to a 500 mL reaction flask, and the reaction was performed at room temperature for 5 hours. After the reaction was completed, the mixture was extracted with an aqueous solution of methylene chloride and Na ₂ CO ₃ , dried over MgSO ₄ , concentrated, and the resulting compound was short-phase column (methylene chloride: hexane = 1: 1) and recrystallized with methylene chloride and hexane 23 g (87%) was obtained.

4a-2(2-bromo-9-phenyl carbazole)의 합성 Synthesis of 4a-2 (2-bromo-9-phenyl carbazole)

Step 1)

Scheme 3

Toluene (250 mL), phenyl boronic acid (10 g, 82 mmol), 2,5-dibromonitrobenzene (23.1 g, 82.3 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.5 mmol) in a 500 mL round bottom flask, Add 2M Na ₂ CO ₃ aqueous solution (124 mL). Thereafter, the mixture was heated to reflux for 6 hours at 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was silicagel column (methylene chloride: hexane = 1: 1) to give 19.2 g (84.2%) of the product.

Step 2)

Scheme 4

In a 250 mL round bottom flask, 4-Bromo-2-nitrobenzene (19.2 g, 69.04 mmol) and triehtyl phosphate (84 mL, 483.28 mmol) were added and heated to reflux for 14 hours at 160 ° C to 165 ° C. After the reaction is completed, the remaining triehtyl phosphite is removed by distillation under reduced pressure, diluted with MeOH: H ₂ O = 1: 1 mixed solvent, and the resulting solid is filtered. The resulting solid is washed with MeOH: H ₂ O = 1: 1 mixed solvent and petroleum ether. The solid was dissolved in methylene chloride, dried over MgSO ₄ , concentrated and silica gel column. (petroleum ether: methylene chloride = 2: 1) 10.2 g (60%) of product is obtained.

Step 3)

Scheme 5

2-Bromocarbazole (6 g, 24.38 mmol), iodobenzene (9.95 g, 48.76 mmol), K ₂ CO ₃ (10.11 g, 73.14 mmol), Cu powder (1.55 g, 24.38 mmol), 18- in a 250 mL round bottom flask. Add crown-6 (3.22 g, 12.19 mmol) and o-dichlorobenzene (150 mL) and reflux for 24 hours. After the reaction was completed, the mixture was extracted with methylene chloride and water, and the obtained organic layer was washed with 5% hydrochloric acid and brine. The organic layer was dried over MgSO 4, concentrated, and the compound was purified by silicagel column (ethyl acetate: hexane = 1: 1) to give 5.5 g (70%) of the product.

출발물질 2의 합성 Synthesis of Starting Material 2

Scheme 6

Synthesis of 2-1 (if same as 1-1 and 1-2)

As can be seen from Scheme 5, one round of compound (1 equiv), amination compound (2 equiv), Pd ₂ (dba) ₃ (0.06 ~ 0.1 mmol), PPh ₃ (0.2 equiv), NaO After adding t- Bu (6 equivalents) and toluene (10.5 mL / 1 mmol), the reaction is carried out at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel c olumn and recrystallized to obtain a product.

Synthesis of 2-2 (if different from 1-1 and 1-2)

As can be seen from Scheme 5, 1 round of compound (1 equivalent), amination compound 1-1 (1 equivalent), Pd ₂ (dba) ₃ (0.05eq), PPh ₃ (0.1 equivalent), NaO t -Bu (3 equiv) and toluene (10.5 mL / 1 mmol) were added, followed by reaction at 100 ° C. After the reaction was completed, the mixture was extracted with ethe r and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel colum n and recrystallized to obtain a product.

Product obtained (1eq), amine compound 1-2 (1 equiv), Pd ₂ (dba) ₃ (0.05eq), PPh ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol ) Is added and the reaction proceeds at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain a product.

5-Bromo-N1- (9,9-dimethyl-9H-fluoren-2-yl) -N1, N3, N3-triphenylben zene-1,3-diamine

Synthesis of

1371,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (1 4.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mm ol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) were reacted with the above 2- The product of 19.44 g (yield: 64%) was obtained using the synthesis method of the following (hereinafter referred to as 'synthesis method of 2-2').

2-Bbromo- N ^4- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ¹ , N ⁴ -triphenylbenzene-1,4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized using the synthesis method of 2-2 above. 18.23 g (yield: 60%) of the product were obtained

5-Bromo-N1- (9,9-diphenyl-9H-fluoren-2-yl) -N1, N3, N3-triphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd ₂ ( dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) using 22.68g synthesis using 2-2 (Yield 62%) of the product was obtained.

N ^1- (9,9'-spirobi [fluorene] -2-yl) -5-bromo- N ¹ , N ³ , N ³ -triphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- phenyl-9,9'-spirobi [fluoren] -2-amine (20.38g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized using the synthesis method of 2-2 above. 23.72 g (yield: 65%) of the product were obtained.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ³ -phenyl- N ¹ , N ³ -di (pyridin-2-yl) benzene-1,3-Diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N -phenylpyridin-2 -amine (8.51 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL ) Was obtained using the synthesis method of 2-2 above to obtain 18.90 g (yield: 62%) of the product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ³ -phenyl- N ¹ , N ³ -di (thiophen-2-yl) benzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiophen-2-amine (14.57 g, 50 mmol), N -phenylthiophen-2 -amine (8.76 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL ) Was obtained using the synthesis method of 2-2 above to obtain 19.52 g (yield: 63%) of the product.

5-Bromo- N ¹ , N ³ -bis (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (28.54g, 100 mmol), Pd ₂ (dba) ₃ (2.3 g, 2.5 mmol), PPh ₃ (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol) and toluene (525 mL) were synthesized according to the above-mentioned 2-1 in Scheme 5. ) To give 24.25 g (yield: 67%) of the product.

2-Bromo- N ¹ , N ⁴ -bis (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ⁴ -diphenylbenzene-1,4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized using the above synthesis method. 23.16 g (yield: 64%) of the product were obtained

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (9,9-diphenyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenylbenzene- 1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N -9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 9,9-dimethyl- N -phenyl-9H- fluoren-2-amine (14.27 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) was used in the synthesis of 2-2 to yield 26.28 g (yield: 62%) of product.

N ^1- (9,9'-spirobi [fluorene] -2-yl) -5-bromo- N ^3- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenyl benzene -1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), 9,9-dimethyl-N-phenyl- 9H-fluoren-2-amine (14.27 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) , toluene (1050 mL) was obtained using the synthesis method of 2-2 to give 26.22 g (yield: 62%) of product.

5-Bromo- N ¹ , N ³ -bis (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -di (pyridin-2-yl) benzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (28.64 g, 100 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) were obtained using 23.59 g (yield) using the synthesis method of 2-1. : 65%) of the product was obtained

5-Bromo- N ¹ , N ³ -bis (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -di (thiophen-2-yl) benzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiphen-2-amine (29.14 g, 100 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) were obtained using 23.18 g (yield) using the above synthesis method. : 63%) of the product was obtained

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenyl-N3-p-tolylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 19.58 g (yield 63%) of product.

2-Bromo- N ^4- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ⁴ -diphenyl-N1-p-tolylbenzene-1,4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 19.89 g (yield: 64%) of product

5-Bromo- N ^1- (9,9-diphenyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenyl- N ³ -p-tolylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N -9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis yielded 23.12 g (yield: 62%) of product.

^{N 1 - (9,9'-spirobi [} fluorene] -2-yl) -5-bromo- N 1, N 3 -diphenyl- N 3 -p-tolylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 23.06 g (yield: 62%) of product

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -di (pyridin-2-yl) -N ³ -p-tolylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl)

pyridin-2-amine (14.32g, 50 mmol), N- p-tolylpyridin-2-amine (9.21 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 above to obtain 19.64 g (yield: 63%) of product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -di (thiophen-2-yl) -N ³ -p-tolylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-l) thiophen-2-amine (14.57 g, 50 mmol), N -p-tolylthiophen -2-amine (9.46 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene ( 1050 mL) was obtained using the synthesis method of 2-2 above to obtain 19.00 g (yield: 60%) of the product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (4-methoxyphenyl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-methoxy- N -phenylaniline (9.96 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) The synthesis method was used to obtain 20.72 g (yield: 65%) of the product.

2-Bromo- N ^4- (9,9-dimethyl-9H-fluoren-2-yl) -N ^1- (4-methoxyphenyl) -N ¹ , N ⁴ -diphenylbenzene-1,4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N -phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-methoxy- N -phenylaniline (9.96 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 19.45 g (yield: 61%) of product

5-Bromo- N ^1- (9,9-diphenyl-9H-fluoren-2-yl) -N ^3- (4-methoxyphenyl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N , 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis yielded 23.23 g (yield: 61%) of product.

N ^1- (9,9'-spirobi [fluorene] -2-yl) -5-bromo- N ^3- (4-methoxyphenyl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Using the synthesis method of 2, 23.06 g (yield: 62%) of the product were obtained.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (4-methoxyphenyl) -N ¹ , N ³ -di (pyridin-2-yl) benzene-1, 3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (4- methoxyphenyl) pyridin-2-amine (10.01 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) , toluene (1050 mL) was obtained using the synthesis method of 2-2 to obtain 19.19 g (yield: 60%) of product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (4-methoxyphenyl) -N ¹ , N ³ -di (thiophen-2-yl) benzene-1, 3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-l) thiophen-2-amine (14.57 g, 50 mmol), N- (4- methoxyphenyl) thiophen-2-amine (10.26 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) , toluene (1050 mL) was obtained using the synthesis method of 2-2 to obtain 19.81 g (yield: 61%) of product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (4-fluorophenyl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-fluoro- N -phenylaniline (9.36 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 18.77 g (yield: 60%) of product

2-Bromo- N ^4- (9,9-dimethyl-9H-fluoren-2-yl) -N ^1- (4-fluorophenyl) -N ¹ , N ⁴ -diphenylbenzene-1,4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-fluoro- N -phenylaniline (9.36 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 18.14 g (yield: 58%) of product

5-Bromo- N ^1- (9,9-diphenyl-9H-fluoren-2-yl) -N ^3- (4-fluorophenyl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N , 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-fluoro- N -phenylaniline (9.36 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis yielded 22.12 g (yield: 59%) of product.

N ^1- (9,9'-spirobi [fluorene] -2-yl) -5-bromo- N ^3- (4-fluorophenyl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), 4-fluoro- N -phenylaniline (9.36 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) 2. The obtained product was obtained in 21.31 g (yield: 57%).

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (4-fluorophenyl) -N ¹ , N ³ -di (pyridin-2-yl) benzene-1, 3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (4- fluorophenyl) pyridin-2-amine (9.41 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) , toluene (1050 mL) was obtained using the synthesis method of 2-2 to give 18.20 g (yield: 58%) of product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (4-fluorophenyl) -N ¹ , N ³ -di (thiophen-2-yl) benzene-1, 3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-l) thiophen-2-amine (14.57 g, 50 mmol), N- (4- fluorophenyl) thiophen-2-amine (9.66 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) , toluene (1050 mL) was obtained using the synthesis method of 2-2 to obtain 19.13 g (yield: 60%) of product.

N ^1- (biphenyl-4-yl) -5-bromo- N ^3- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N- phenylbiphenyl-4-amine (12.27 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Using the synthesis method of 2 to obtain 23.25 g (yield: 68%) of the product.

N ^1- (biphenyl-4-yl) -2-bromo- N ^4- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ⁴ -diphenylbenzene-1,4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N- phenylbiphenyl-4-amine (12.27 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 21.88 g (yield: 64%) of product

N ^1- (biphenyl-4-yl) -5-bromo- N ^3- (9,9-diphenyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N , 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N -phenylbiphenyl-4-amine (12.27 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis gave 25.45 g (yield 63%) of product.

N ^1- (9,9'-spirobi [fluorene] -2-yl) -N ^3- (biphenyl-4-yl) -5-bromo- N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), N -phenylbiphenyl-4-amine (12.27 g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Using the synthesis method of 2, 25.79 g (yield: 64%) of the product were obtained.

N ^1- (biphenyl-4-yl) -5-bromo- N ^3- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -di (pyridin-2-yl) benzene- 1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (biphenyl- 4-yl) pyridin-2-amine (12.32 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 to give 21.26 g (yield: 62%) of product.

N ^1- (biphenyl-4-yl) -5-bromo- N ^3- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -di (thiophen-2-yl) benzene- 1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-l) thiophen-2-amine (14.57 g, 50 mmol), N- (biphenyl- 4-yl) thiophen-2-amine (12.57 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 to give 21.57 g (yield: 62%) of product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (naphthalen-1-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N- phenylnaphthalen-1-amine (10.96g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 22.03 g (yield 67%) of product.

2-Bromo- N ^4- (9,9-dimethyl-9H-fluoren-2-yl) -N ^1- (naphthalen-1-yl) -N ¹ , N ⁴ -diphenylbenzene-1,4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N- phenylnaphthalen-1-amine (10.96g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 21.37 g (yield: 65%) of product.

5-Bromo- N ^1- (9,9-diphenyl-9H-fluoren-2-yl) -N ^3- (naphthalen-1-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N , 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N -phenylnaphthalen-1-amine (10.96g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis yielded 24.63 g (yield 63%) of product.

N ^1- (9,9'-spirobi [fluorene] -2-yl) -5-bromo- N ^3- (naphthalen-1-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), N -phenylnaphthalen-1-amine (10.96g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 25.34 g (yield: 65%) of product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (naphthalen-1-yl) -N ¹ , N ³ -di (pyridin-2-yl) benzene- 1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (naphthalen- 1-yl) pyridin-2-amine (11.01 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 to give 21.11 g (yield: 64%) of product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (naphthalen-1-yl) -N ¹ , N ³ -di (thiophen-2-yl) benzene- 1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiophen-2-amine (14.57 g, 50 mmol), N- (naphthalen- 1-yl) thiophen-2-amine (11.27 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol ), toluene (1050 mL) was obtained using the synthesis method of 2-2 above to obtain 20.43 g (yield: 61%) of the product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (naphthalen-2-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N- phenylnaphthalen-2-amine (10.96g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 21.70 g (yield: 66%) of product.

2-Bromo- N ^4- (9,9-dimethyl-9H-fluoren-2-yl) -N ^1- (naphthalen-2-yl) -N ¹ , N ⁴ -diphenylbenzene-1,4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N- phenylnaphthalen-2-amine (10.96g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 21.04 g (yield: 64%) of product.

5-Bromo- N ^1- (9,9-diphenyl-9H-fluoren-2-yl) -N ^3- (naphthalen-2-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N , 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N -phenylnaphthalen-2-amine (10.96g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis yielded 25.41 g (yield: 65%) of product.

N ^1- (9,9'-spirobi [fluorene] -2-yl) -5-bromo- N ^3- (naphthalen-2-yl) -N ¹ , N ³ -diphenylbenzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), N- phenylnaphthalen-2-amine (10.96g , 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Synthesis of 2 gave 24.56 g (yield: 63%) of product.

* 5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (naphthalen-2-yl) -N ¹ , N ³ -di (pyridin-2-yl) benzene -1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (naphthalen- 2-yl) pyridin-2-amine (11.01 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 to give 21.11 g (yield: 64%) of product.

5-Bromo- N ^1- (9,9-dimethyl-9H-fluoren-2-yl) -N ^3- (naphthalen-2-yl) -N ¹ , N ³ -di (thiophen-2-yl) benzene- 1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiophen-2-amine (14.57 g, 50 mmol), N- (naphthalen- 2-yl) thiophen-2-amine (11.27 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol ), toluene (1050 mL) was purified using the synthesis method of 2-2 to yield 20.76 g (yield: 62%) of product.

5-Bromo- N ^1- (dibenzo [b, d] thiophen-2-yl) -N ^3- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenylbenzene-1, 3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenyldibenzo [b, d] thiophen- 2-amine (13.77g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) was used for the synthesis of 2-2 to yield 23.20 g (yield: 65%) of product.

2-Bromo- N ^1- (dibenzo [b, d] thiophen-2-yl) -N ^4- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ⁴ -diphenylbenzene-1, 4-diamine

Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl- N- phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenyldibenzo [b, d] thiophen- 2-amine (13.77g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) was used for the synthesis of 2-2 to yield 22.48 g (yield: 63%) of product.

5-Bromo- N ^1- (dibenzo [b, d] thiophen-2-yl) -N ^3- (9,9-diphenyl-9H-fluoren-2-yl) -N ¹ , N ³ -diphenylbenzene-1, 3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N , 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenyldibenzo [b, d] thiophen-2- amine (13.77 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) Using the synthesis method of 2-2 to give 28.07 g (yield: 67%) of the product.

N ^1- (9,9'-spirobi [fluorene] -2-yl) -5-bromo- N ^3- (dibenzo [b, d] thiophen-2-yl) -N ¹ , N ³ -diphenylbenzene-1, 3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), N-phenyldibenzo [b, d] thiophen- 2-amine (13.77g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol), toluene (1050 mL) was used to synthesize 27.17 g (yield: 65%) of the product.

5-Bromo- N ^1- (dibenzo [b, d] thiophen-2-yl) -N ^3- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -di (pyridin- 2-yl) benzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (dibenzo [ b, d] thiophen-2-yl) pyridin-2-amine (13.82 g, 50 mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 above to give 21.47 g (yield: 60%) of product.

[Revision under Rule 91 09.11.2011]
5-Bromo- N ^1- (dibenzo [b, d] thiophen-2-yl) -N ^3- (9,9-dimethyl-9H-fluoren-2-yl) -N ¹ , N ³ -di (thiophen- 2-yl) benzene-1,3-diamine

Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiophen-2-amine (14.57 g, 50 mmol), N- (thiophen- 2-yl) dibenzo [b, d] thiophen-2-amine (14.07g, 50mmol), Pd ₂ (dba) ₃ (4.58 g, 5 mmol), PPh ₃ (2.62 g, 10 mmol), NaO t -Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using 22.86 g (yield: 63%) of the product using the above synthesis method.

Synthesis method of final compound

Scheme 7

[Revision under Rule 91 09.11.2011]

As can be seen from Scheme 6, Compound 4 (1 equiv), 2 compounds (1.1 equiv), Pd (PPh ₃ ) ₄ (0.03-0.05 equiv), NaOH (3 equiv), THF ( 3 mL / 1 mmol) and water (1.5 mL / 1 mmol).

After that, the mixture is heated to reflux at 80 ° C to 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain a product. The product was confirmed by FD-MS as shown in Table 1 below.

In general, the final compounds can be analyzed by nuclear magnetic resonance (NMR), mass spectrometry (Mass). However, the above-mentioned final compounds have many aromatic structures, so the structure was analyzed by mass spectrometry (Mass) rather than nuclear magnetic resonance (NMR).

In this case, FD-MS means mass spectrometer. When mass spectrometry is performed, mass peaks appear as the final compounds are broken, and m / z means the peak. In other words, m / z means the mass spectrometry main peck of the above-mentioned final compounds. This can confirm the presence of the compounds.

TABLE 1

In this case, the compounds represented by the formula (1) is a synthesis of the compounds represented by the formula (3) X or R ₃ -R _7, R ₁ and R ₂ , R 'and R''of the formula or substituted or unsubstituted substituents in a broad relationship Examples are described by way of example, but the compounds represented by Formula 1, which are not described by way of example as synthetic examples, may also form part of the present specification.

유기 EL 소자의 제조 평가Manufacturing evaluation of organic electroluminescent element

Various compounds obtained through synthesis were used as light emitting host materials or hole transporting layers of the light emitting layer, respectively, to fabricate an organic light emitting device according to a conventional method.

First, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter 2T-NATA) as a hole injection layer on the ITO layer (anode) formed on the glass substrate first The film was vacuum deposited to form a thickness of 10 nm.

Subsequently, one of the compounds represented by Formulas 1 to 3 as the hole transport compound was vacuum deposited to a thickness of 30 nm to form a hole transport layer. After the formation of the hole transport layer, when the developed material was measured by the hole transport layer, a light emitting layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X was a blue fluorescent dopant) 9,10-di (naphthalene-2-anthracene (AND)) was used as the light emitting host material.

(1,1'bisphenyl) -4-oleato) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm in a hole blocking layer, followed by electron Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was formed into an injection layer to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

Comparative Experiment

When the compounds of the present invention were measured by the hole transport layer, an organic electric field having the same structure as in the experimental example was prepared by using a compound represented by the following Chemical Formula 4 (hereinafter abbreviated as NPB) as a hole transport material instead of the compound of the present invention for comparison. A light emitting device was manufactured.

[Formula 4]

TABLE 2

As can be seen from the results of Table 2, the organic electroluminescent device using the organic electroluminescent device material of the present invention has high efficiency and color purity as well as long life blue light emission is obtained as a hole transporting material of the organic electroluminescent device Can be used to significantly improve the low driving voltage, high luminous efficiency and lifetime.

Even if the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a hole transport layer as well as a light emitting layer, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained. .

In this case, the compounds represented by the formula (1) is a substituted or unsubstituted substituents of X, R ₃ -R _7, R ₁ and R ₂ , R 'and R''of the formula (1) Some comparative examples have been described by way of example, but the compounds represented by the formula (1), which are not illustratively described as comparative examples, also exhibit the same effects as the above-described comparative examples because of the parent nucleus structure of the formula (1). The results may form part of the specification.

Preparation Example 2

Hereinafter, the preparation or synthesis examples of the compound belonging to the formulas (1) to (3) containing deuterium and tritium will be described. However, since the number of compounds belonging to the formulas 1 to 3 containing deuterium and tritium is large, one or two of the compounds belonging to formulas 1 to 3 including deuterium and tritium will be described. Those skilled in the art to which the present invention pertains, that is, those skilled in the art can prepare the compounds belonging to the present invention which are not illustrated through the preparation examples described below.

In other words, as can be seen from Scheme 8, after the intermediate 1) to intermediate 5) was synthesized using the intermediates of the present invention (B-1 to B-8, C-1 to C-8) ) Compounds can be synthesized. Detailed description thereof will be described below in detail.

Scheme 8

Synthesis of Intermediates

Synthesis of Intermediate 1)

9-phenyl-9H-carbazole (20 g, 82.203 mmol), NBS (48.84 g, 172.63 mmol) and BPO (1.99 g, 8.22 mmol) were added to the 1L round bottom flask, followed by methylene chloride (246 mL). Stir at room temperature for 5-7 hours. After the reaction is completed, the organic layer is extracted with methylene chloride and water, dried over MgSO ₄ and the organic solvent is removed. After silicagel column, recrystallized with dichloromethane and hexane to give 28.7 g of the title compound as a solid. Yield: 87%, FD-MS: m / z = 398.93 (C ₁₈ H ₁₁ Br ₂ N = 401.09)

Synthesis of Intermediate 2)

In a 1L round bottom flask, add Formula 1 (28.7 g, 71.56 mmol) to 200 mL of anhydrous THF, lower the temperature to -78 ° C, and add n-BuLi (2.5M in hexane, 34.35 mL, 85.9 mmol) for 1 hour. Stir while. Then add D2O (2.14 g, 107.15 mmol), warm to room temperature and stir for 1 hour. H2O (48 mL) was added at room temperature, and after stirring, the organic layer was extracted and separated. The organic layer is dried over MgSO ₄ and the organic solvent is removed. After silicagel column, recrystallized with dichloromethane and hexane to give 11.56 g of the title compound as a solid. Yield: 50%, FD-MS: m / z = 322.02 (C ₁₈ H ₁₁ DBrN = 323.20)

Synthesis of Intermediate 3)

Add Formula 2 (11.56 g, 35.77 mmol) and dissolve in 110 mL of anhydrous THF and lower the temperature to -78 ° C. Then slowly add dropwise n-BuLi (2.5M in hexane, 40.2 mL, 37.56 mmol). Stir at -78 ° C for 1.5 hours. triisopropyl borate (24.7 mL, 107.31 mmol) is slowly added dropwise. Slowly raise the temperature to room temperature and overnight at room temperature. 10% HCl aqueous solution is added after completion of the reaction. The resulting solid was filtered and washed with hexane to give 6.7 g of the title compound as a solid. Yield: 65%, FD-MS: m / z = 288.12 (C ₁₈ H ₁₃ DBNO ₂ = 288.13)

Synthesis of Intermediates 4) and 5)

Intermediates 4) and 5) obtained the final material in the same manner as the synthesis method of the above-described intermediates except that T2O was used instead of D2O.

최종화합물의 합성방법Synthesis method of final compound

Scheme 9

[Revision under Rule 91 09.11.2011]

Compound (1 equiv), 2 compounds (1.1 equiv), Pd (PPh ₃ ) ₄ (0.03-0.05 equiv), NaOH (3 equiv), THF (3 mL / 1 mmol), water (1.5) in a round bottom flask mL / 1 mmol).

After that, the mixture is heated to reflux at 80 ° C to 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product by FD-MS as shown in Table 3 below. B-8, C-1 to C-8) compounds) were identified.

TABLE 3

Various compounds obtained through synthesis were used as light emitting host materials or hole transporting layers of the light emitting layer, respectively, to fabricate an organic light emitting device according to a conventional method. First, 4,4 ', 4' '-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter 2T-) as a hole injection layer on the ITO layer (anode) formed on the glass substrate. Abbreviated as NATA) film was vacuum deposited to form a thickness of 10 nm.

Subsequently, embodiments of the present invention as a hole transport compound (B-1, B-2, B-4, B-5, B-8, C-1, C-2, C-4, C-5, C One of the compounds of -8) was vacuum deposited to a thickness of 30 nm to form a hole transport layer. After the formation of the hole transport layer, when the developed material was measured by the hole transport layer, a light emitting layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X was a blue fluorescent dopant) 9,10-di (naphthalene-2-anthracene (AND)) was used as the light emitting host material.

(1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to an electron injection layer at a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

Comparative Experiment 2

Compounds of Embodiments of the Invention (B-1, B-2, B-4, B-5, B-8, C-1, C-2, C-4, C-5, C-8) When one of the measured by the hole transport layer, embodiments of the present invention (B-1, B-2, B-4, B-5, B-8, C-1, C-2, C- for comparison) 4, C-5, C-8) instead of one of the compounds represented by the following formula (hereinafter abbreviated as NPB) was used as a hole transport material to fabricate an organic EL device having the same structure as the experimental example .

TABLE 4

As can be seen from the results of Table 2, the organic electroluminescent device using the organic electroluminescent device material of the present invention is not only high efficiency and color purity but also blue light emission with long life is obtained as a hole transporting material of the organic light emitting device Can be used to significantly improve the low driving voltage, high luminous efficiency and lifetime.

The above description is merely illustrative of the present invention, and those skilled in the art will appreciate that various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments.

The scope of protection of the present invention should be interpreted by the following claims, and all the technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATIONCROSS-REFERENCE TO RELATED APPLICATION

This patent application is related to the patent application No. 10-2010-0095402 filed in Korea on September 30, 2010 and the patent application No. 10-2011-0018801 filed in Korea on March 3, 2011. Priority is claimed under section (a) (35 USC § 119 (a)), all of which is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason as above for a country other than the United States, all the contents thereof are incorporated into this patent application by reference.

Claims

Compound represented by the following formula (1):

Formula 1

In Chemical Formula 1, the Cz group is a substituted or unsubstituted carbazole derivative which may be represented by the following Chemical Formula 2,

Formula 2

R 3 -R 7 , X, which may be substituted on the carbon atom of carbazole in Formula 2, may be the same or different from each other independently of each other hydrogen, deuterium, tritium; Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, S, N, O, P and Si Substituted or unsubstituted hetero aryl group having 5 to 60 carbon atoms, substituted or unsubstituted A substituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted nuclear C5-C60 aryloxy group, a substituted or unsubstituted C5-C60 aryl cy Or an amino group, a halogen atom, a cyano group, a nitro group, a hydroxyl group substituted with an alkoxycarbonyl group having 5 to 60 carbon atoms substituted or unsubstituted, or an aryl group having 5 to 60 substituted carbon atoms substituted or unsubstituted, or Carboxyl group, and the like, m is an integer of 1 to 3,

Ar 1 to Ar 3 in Formula 1 may be the same as or different from each other, each independently substituted or unsubstituted aryl group having 3 to 60 nuclear atoms, or at least one hetero of S, N, O, P and Si A substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms including an atom, a substituted or unsubstituted alkyl group, and R 1 and R 2 , R ′ and R ″ may be the same as or different from each other. Independently hydrogen, deuterium, tritium; Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one heteroatom of S, N, O, P and Si, substituted or Unsubstituted C1-C60 alkyl group, substituted or unsubstituted C1-C60 alkoxy group, substituted or unsubstituted nuclear C5-C60 aryloxy group, substituted or unsubstituted C5-C60 aryl A thio group, a substituted or unsubstituted alkoxycarbonyl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a halogen atom, a cyano group, a nitro group, a hydroxyl group or Carboxyl group and the like.
The method of claim 1,

The R 3 -R 7 may be bonded to each other adjacent groups to form a ring (ring), Ar 1 ~ Ar 3 may be bonded to each other adjacent groups to form a ring (ring), R 1 and R 2 , R 'and R''is a compound characterized in that adjacent groups can combine with each other to form a ring.
The method of claim 1,

Ar 1 to Ar 3 is selected from the group consisting of a substituted or unsubstituted phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, fluorene group, thiophene group, pyrrole group, furan group, pyridyl group Characterized by a compound.
The method of claim 1,

Compound represented by Formula 1 is one of the compounds represented by Formula 3 below:

Formula 3
An organic electric device comprising at least one organic material layer containing any one of the compounds according to any one of claims 1 to 4.
The method of claim 5,

The organic electroluminescent device, characterized in that to form the organic material layer by a solution process (soluble process).
The method of claim 5,

The organic electronic device is characterized in that it comprises a first electrode, the at least one organic material layer and the second electrode in a stacked form sequentially.
The method of claim 7, wherein

The organic material layer is an organic electric device, characterized in that any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
The method of claim 7, wherein

The organic material layer includes a light emitting layer,

The organic electroluminescent device according to claim 1, wherein the compound is used as a host or dopant material in the light emitting layer.
A display device comprising the organic electric element of claim 7;

And a control unit for driving the display device.
The method of claim 10,

The organic electroluminescent device is an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC) drum, characterized in that one of the organic transistor (organic TFT).