KR101782881B1 - Organic compound and organic optoelectric device and display device - Google Patents

Abstract

상기 화학식 1에서, X, R¹ 내지 R¹², L¹ 내지 L⁶, n¹ 내지 n⁴, Ar¹ 및 Ar²는 명세서에서 정의한 바와 같다. An organic optoelectronic device using the organic compound, and a display device including the organic optoelectronic device.
[Chemical Formula 1]

In Formula 1, X, R ¹ to R ¹² , L ¹ to L ⁶ , n ¹ to n ⁴ , Ar ¹ and Ar ² are as defined in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic compound, an organic optoelectronic device,

Organic optoelectronic devices, and display devices.

Organic optoelectronic devices are devices that can switch between electrical and optical energy.

Organic optoelectronic devices can be roughly classified into two types according to the operating principle. One is an optoelectronic device in which an exciton formed by light energy is separated into an electron and a hole, the electron and hole are transferred to different electrodes to generate electric energy, and the other is a voltage / Emitting device that generates light energy from energy.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light emitting devices, organic solar cells, and organic photo conductor drums.

In recent years, organic light emitting diodes (OLEDs) have attracted considerable attention due to the demand for flat panel display devices. The organic light emitting diode is a device for converting electrical energy into light by applying an electric current to the organic light emitting material, and usually has an organic layer inserted between an anode and a cathode.

The performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and the organic layer is highly affected by the organic material contained in the organic layer. In particular, in order for the organic light emitting device to be applied to a large-sized flat panel display device, it is necessary to develop an organic material capable of increasing the mobility of holes and electrons and increasing the electrochemical stability.

One embodiment provides an organic compound capable of realizing a high-efficiency and long-lived organic optoelectronic device.

Another embodiment provides an organic optoelectronic device comprising the organic compound.

Another embodiment provides a display device comprising the organic opto-electronic device.

According to one embodiment, there is provided an organic compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

Two of X are N, two are C,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,

R ⁵ to R ¹² each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,

L ¹ to L ⁶ each independently represent a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group or a substituted or unsubstituted quaterphenylene group,

n ¹ to n ⁴ each independently represents an integer of 0 to 5,

the sum of n ¹ to n ⁴ is an integer of 2 or more,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group, a group represented by the formula A, a group represented by the formula B, or a combination thereof,

At least one of Ar ¹ and Ar ² is a group represented by the following formula (A), a group represented by the following formula (B)

 (A)

In the above formula (A)

Y is O, S, CR ^a R ^b , SiR ^c R ^d or NR ^e ,

R ¹³ to R ²⁰ and R ^a to R ^e each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocycle A combination thereof, or a linking point with L ⁵ or L ⁶ in the above formula (1)

R ¹³ to R ²⁰ are each independently present or two adjacent ones are connected to each other to form a fused ring,

[Chemical Formula B]

In the above formula (B)

R ²¹ to R ³⁰ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,

R ²¹ to R ³⁰ are each independently present or two adjacent ones are connected to form a fused ring,

* Is the point of connection with L ⁵ or L ⁶ in formula (1).

According to another embodiment, there is provided an organic optoelectronic device including an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, wherein the organic layer includes the organic compound.

According to another embodiment, there is provided a display device including the organic optoelectronic device.

High-efficiency long-lived organic optoelectronic devices can be realized.

1 and 2 are sectional views showing an organic light emitting device according to an embodiment, respectively.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, at least one of the substituents or at least one hydrogen in the compound is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, A C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C6 to C30 heterocyclic ring, a C1 to C20 alkoxy group, A C1 to C10 trifluoroalkyl group such as a fluoro group or a trifluoromethyl group, or a cyano group.

A substituted or unsubstituted C1 to C20 amine group, a nitro group, a substituted or unsubstituted C3 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C10 alkylsulfinyl group, A C1 to C10 trifluoroalkyl group such as a C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C6 to C30 heterocyclic ring, a C1 to C20 alkoxy group, a fluoro group or a trifluoromethyl group, or a cyano group Two adjacent substituents may be fused to form a ring. For example, the substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

As used herein, "hetero" means that at least one heteroatom selected from the group consisting of N, O, S, P and Si is contained in one functional group and the remainder is carbon, unless otherwise defined .

As used herein, the term "aryl" means a substituent in which all the elements of the cyclic substituent have p-orbital, and these p-orbital forms conjugation, and monocyclic, Fused ring polycyclic (i. E., Rings that divide adjacent pairs of carbon atoms) functional groups.

As used herein, the term " heterocyclic group "includes at least one heteroatom selected from the group consisting of N, O, S, P, and Si in a ring compound such as an aryl group or a cycloalkyl group, Carbon. When the heterocyclic ring is a fused ring, the heterocyclic group or the ring may include one or more heteroatoms.

More specifically, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heterocyclic group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthra A substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted naphthacenyl group, A substituted or unsubstituted aryl group, a substituted m-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group , A substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted pyrazolyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group , A substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzothiophenyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group , A substituted or unsubstituted benzoxazine group, a substituted or unsubstituted benzothiazine group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazine group, a substituted or unsubstituted A substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted pyrazolyl group, , Combinations thereof, or combinations thereof, but are not limited thereto.

In the present specification, the hole property refers to a property of forming holes by donating electrons when an electric field is applied, and has a conduction property along the HOMO level so that the injection of holes formed in the anode into the light emitting layer, Quot; refers to the property of facilitating the movement of the hole formed in the light emitting layer to the anode and the movement of the hole in the light emitting layer.

In addition, the electron characteristic refers to a characteristic that electrons can be received when an electric field is applied. The electron characteristic has a conduction characteristic along the LUMO level so that electrons formed in the cathode are injected into the light emitting layer, electrons formed in the light emitting layer migrate to the cathode, It is a characteristic that facilitates movement.

The organic compounds according to one embodiment will be described below.

The organic compound according to one embodiment is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

Two of X are N, two are C,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,

R ⁵ to R ¹² each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,

L ¹ to L ⁶ each independently represent a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group or a substituted or unsubstituted quaterphenylene group,

n ¹ to n ⁴ each independently represents an integer of 0 to 5,

the sum of n ¹ to n ⁴ is an integer of 2 or more,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group, a group represented by the formula A, a group represented by the formula B, or a combination thereof,

At least one of Ar ¹ and Ar ² is a group represented by the following formula (A), a group represented by the following formula (B)

 (A)

In the above formula (A)

Y is O, S, CR ^a R ^b , SiR ^c R ^d or NR ^e ,

R ¹³ to R ²⁰ and R ^a to R ^e each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocycle A combination thereof, or a linking point with L ⁵ or L ⁶ in the above formula (1)

R ¹³ to R ²⁰ are each independently present or two adjacent ones are connected to each other to form a fused ring,

[Chemical Formula B]

In the above formula (B)

R ²¹ to R ³⁰ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,

R ²¹ to R ³⁰ are each independently present or two adjacent ones are connected to form a fused ring,

* Is the point of connection with L ⁵ or L ⁶ in formula (1).

The organic compound represented by Formula 1 includes a substituted or unsubstituted benzoquinazoline containing two nitrogen atoms and a substituted or unsubstituted phenylene group having two or more meta bonds.

The nitrogen moiety of the substituted or unsubstituted benzoquinazoline has polarity and can interact with the electrode, thereby facilitating charge injection and enhancing charge mobility by means of three fused rings.

In addition, the substituted or unsubstituted benzoquinazoline has a relatively low LUMO energy level, which facilitates electron injection and can improve thermal stability and electrical stability. The substituted or unsubstituted benzoquinazoline may have, for example, a LUMO energy level of about 1.7 to 2.1 eV.

The two or more meta-bonded substituted or unsubstituted phenylene groups can increase the stability of the benzoquinazoline by appropriately controlling the flow of charges moving toward the benzoquinazoline side. In particular, it is possible to reduce the oxidation of the carbons of the ring adjacent to the nitrogen-containing ring of the benzoquinazoline, that is, the carbons to which R ³ or R ⁴ are bonded, thereby enhancing the stability of the organic compound. Thus, the lifetime of the organic compound can be improved.

In one example, R ³ or R ⁴ may each independently be hydrogen.

The two or more meta-bonded substituted or unsubstituted phenylene groups may be located on one side of the benzoquinazoline or on both sides of the benzoquinazoline. For example, the two or more meta-bonded substituted or unsubstituted phenylene groups may be located on both sides of the benzoquinazoline. For example, n ¹ and n ² in Formula 1 may independently be 1 to 5.

Also, since the structure of the organic compound has the steric hindrance characteristic, the interaction with neighboring molecules can be suppressed to reduce the crystallization, thereby improving the efficiency and lifetime characteristics.

The organic compound represented by Formula 1 includes at least one of the group represented by Formula A and the group represented by Formula B at the terminal.

The group represented by the formula (A) and the group represented by the formula (B) are groups having a hole characteristic which is susceptible to holes, and are included together with the substituted or unsubstituted benzoquinazoline to form a bipolar structure, So that the efficiency of the organic optoelectronic device to which the organic compound is applied can be improved.

The benzoquinazoline moieties which are susceptible to electrons centering on the linking groups (L ¹ to L ⁶ ) and / or the phenylene moieties and the moieties susceptible to holes are appropriately localized in the compound of the bipolar structure described above and the flow of the conjugated system Control can exhibit excellent bipolar characteristics. Accordingly, the lifetime of the organic optoelectronic device to which the organic compound is applied can be improved.

The organic compound may have a molecular weight of, for example, about 500 or more. When the organic compound is applied to the device by increasing the glass transition temperature (Tg) of the organic compound by having the molecular weight, the stability of the compound during the process can be improved and deterioration can be prevented. Within the above range, for example, from about 500 to 1000, and within this range, for example, from about 550 to 800.

The glass transition temperature (Tg) may be related to the thermal stability of the organic compound and the device to which it is applied. That is, when an organic compound having a high glass transition temperature (Tg) is applied to an organic light emitting device in the form of a thin film, it is prevented from being deteriorated by a temperature in a subsequent process such as an encapsulation process performed after the organic compound is deposited So that the lifetime characteristics of the organic compound and the device can be secured.

The glass transition temperature (Tg) of the organic compound may be, for example, about 70 ° C or more, and more preferably 90 ° C or more within the above range. Within the above range, for example, from about 70 ° C to 150 ° C, and within this range, from about 90 ° C to 130 ° C.

The organic compound may be represented by the following formula 2 or 3 according to the position of nitrogen (N) of benzoquinazoline.

(2)

(3)

In the general formula (2) or (3), R ¹ to R ¹² , L ¹ to L ⁶ , n ¹ to n ⁴ , Ar ¹ and Ar ² are as described above.

The formula (2) may be represented, for example, by the following formula (2A), and the formula (3) may be represented by, for example,

[Chemical Formula 2A]

In Formulas (2A) and (3A), R ¹ to R ⁸ , L ¹ to L ⁴ , n ¹ to n ⁴ , Ar ¹ and Ar ² are as described above.

In Formulas 1 to 3, 2A and 3A, L ¹ to L ⁶ may be, for example, a single bond or one of the groups listed in Group 1 below.

[Group 1]

In the group 1,

R ³¹ to R ³⁴ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,

* Is the connection point.

For example, in the group 1, R ³¹ to R ³⁴ may each independently be hydrogen.

As described above, at least one of Ar ¹ and Ar ² in Formulas 1 to 3, 2A and 3A may be a group represented by Formula A, a group represented by Formula B, or a combination thereof.

For example, the group represented by the above formula (A) may be one of the groups listed in the following group 2, for example.

[Group 2]

In the group 2,

R ³⁵ to R ³⁹ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,

* Is the connection point.

For example, the formula (B) may be one of the groups listed in the following group 3, for example.

[Group 3]

In the group 3,

R ⁴⁰ to R ⁴⁷ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,

* Is the connection point.

The organic compound may be, for example, a compound listed in the following Group 4, but is not limited thereto.

[Group 4]

The above-described organic compounds can be applied to organic optoelectronic devices.

The above-described organic compounds can be applied to organic optoelectronic devices alone or together with other organic compounds.

The organic optoelectronic device is not particularly limited as long as it is an element capable of converting electric energy and optical energy. Examples of the organic optoelectronic device include organic light emitting devices, organic solar cells, and organic photoconductor drums.

The organic optoelectronic device may include an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, and the organic layer may include the organic compound described above.

Here, an organic light emitting device, which is an example of an organic optoelectronic device, will be described with reference to the drawings.

1 and 2 are cross-sectional views illustrating an organic light emitting device according to an embodiment.

1, an organic light emitting device 100 according to an exemplary embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 disposed between the anode 120 and the cathode 110 .

The anode 120 may be made of a conductor having a high work function to facilitate, for example, hole injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 is made of a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of ZnO and Al or a metal and an oxide such as SnO ₂ and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene), polypyrrole and polyaniline, It is not.

The cathode 110 may be made of a conductor having a low work function, for example, to facilitate electron injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 is made of a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium or the like or an alloy thereof; Layer structure materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al and BaF ₂ / Ca.

The organic layer 105 includes the light-emitting layer 130 including the above-described organic compound.

The light-emitting layer 130 may include, for example, the above-described organic compound alone or a mixture of at least two of the organic compounds described above. The organic compound may be used as a host of the light emitting layer 130, and may further include one or more dopants.

The dopant may be a material such as a metal complex that emits light by a multiple excitation which is excited by a triplet state. The dopant may be, for example, an inorganic, organic, or organic compound, and may include one or more species.

Examples of the phosphorescent dopant include organic metal compounds including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh and Pd or combinations thereof. The phosphorescent dopant may be, for example, a compound represented by the following formula (Z), but is not limited thereto.

(Z)

L ₂ MX

In the above formula (Z), M is a metal, L and X are the same or different from each other and are ligands that complex with M.

M may be Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or combinations thereof, Lt; / RTI >

Referring to FIG. 2, the organic light emitting diode 200 further includes a hole-assist layer 140 in addition to the light-emitting layer 130. The hole auxiliary layer 140 can further enhance hole injection and / or hole mobility between the anode 120 and the light emitting layer 130 and block electrons. The hole-assist layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer.

1 or 2, the organic layer 105 may further include an electron transport layer, an electron injection layer, a hole injection layer, and the like.

The organic light emitting devices 100 and 200 may be formed by forming an anode or a cathode on a substrate and then forming an organic layer by a dry film forming method such as evaporation, sputtering, plasma plating, or ion plating, A negative electrode or a positive electrode.

The organic light emitting device described above can be applied to an organic light emitting display.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

Synthesis of organic compounds

[Representative synthesis method]

Synthesis of intermediates

Synthetic example  1: Synthesis of intermediate I-1

[Reaction Scheme 1]

3-bromobenzaldehyde (127 g, 684 mmol) and sodium hydroxide (41.0 g, 1026 mmol) were added to the solution, and the mixture was stirred at room temperature for 2 hours. Respectively. After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Thus, Intermediate I-1 (179 g, 83%) was obtained.

HRMS (70 eV, EI +): m / z calcd for C17H13BrO: 312.0150, found: 312.

Elemental Analysis: C, 65%; H, 4%

Synthetic example  2: Synthesis of intermediate I-2

[Reaction Scheme 2]

3-bromobenzimidamide hydrochloride (128 g, 543 mmol) and sodium hydroxide (65.2 g, 1,629 mmol) were dissolved in ethanol (1.5 L) under nitrogen atmosphere. Lt; / RTI > After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Intermediate I-2 (120 g, 45%) was thus obtained.

HRMS (70 eV, EI +): m / z calcd for C24H16Br2N2: 489.9680, found: 490.

Elemental Analysis: C, 59%; H, 3%

Synthetic example  3: Synthesis of Intermediate I-3

[Reaction Scheme 3]

Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 101 g, 223 mmol) was dissolved in 1 L of monochlorobenzene (MCB) 446 mmol), and the mixture was refluxed by heating at 130 DEG C for 15 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The obtained residue was purified by flash column chromatography to obtain Intermediate I-3 (76.5 g, 70%).

HRMS (70 eV, EI +): m / z calcd for C24H14Br2N2: 487.9524, found: 488.

Elemental Analysis: C, 59%; H, 3%

Synthetic example  4: Synthesis of intermediate I-4

[Reaction Scheme 4]

(100 g, 684 mmol) was dissolved in ethanol (1 L), and benzaldehyde (72.6 g, 684 mmol) and sodium hydroxide (41.0 g, 1026 mmol) were added thereto under nitrogen atmosphere and stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Intermediate I-4 (139 g, 87%) was thus obtained.

HRMS (70 eV, EI +): m / z calcd for C17H14O: 234.1045, found: 234.

Elemental Analysis: C, 87%; H, 6%

Synthetic example  5: Synthesis of intermediate I-5

[Reaction Scheme 5]

3-bromobenzimidamide hydrochloride (131 g, 555 mmol) and sodium hydroxide (66.6 g, 1,665 mmol) were added to ethanol (1.5 L) in a nitrogen atmosphere. Lt; / RTI > After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Intermediate I-5 (115 g, 50%) was thus obtained.

HRMS (70 eV, EI +): m / z calcd for C24H17BrN2: 412.0575, found: 412.

Elemental Analysis: C, 70%; H, 4%

Synthetic example  6: Synthesis of Intermediate I-6

[Reaction Scheme 6]

1,2-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 121 g, 266 mmol) was dissolved in 1.2 L of monochlorobenzene (MCB) 532 mmol), and the mixture was heated at 130 캜 for 15 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-6 (72.2 g, 66%).

HRMS (70 eV, EI +): m / z calcd for C24Hi5BrN2: 410.0419, found: 410.

Elemental Analysis: C, 70%; H, 4%

Synthetic example  7: Synthesis of Intermediate I-7

[Reaction Scheme 7]

1-bromo-3-iodobenzene (170 g, 598 mmol) and tris (diphenylideneacetone) dipalladium (o) (100 g, 598 mmol) were dissolved in 1 L of tetrahydrofuran 5.5 g, 5.98 mmol), tris-tert-butylphosphine (4.8 g, 23.92 mmol) and sodium tert-butoxide (69 g, 717 mmol) were successively added and refluxed by heating at 100 ° C for 18 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-7 (181 g, 94%).

HRMS (70 eV, EI +): m / z calcd for C18H12BrN: 321.0153, found: 321.

Elemental Analysis: C, 67%; H, 4%

Synthetic example  8: Synthesis of Intermediate I-8

[Reaction Scheme 8]

The intermediate 1-7 (50 g, 155 mmol) was dissolved in 1 L of THF in a nitrogen atmosphere followed by the addition of 3-chlorophenyl boronic acid (24 g, 155 mmol) and tetrakis (triphenylphosphine) palladium mmol) were added and stirred. Saturated water-saturated potassium carbonate (54 g, 388 mmol) was added and the mixture was refluxed by heating at 80 ° C for 12 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-8 (51 g, 92%).

HRMS (70 eV, EI +): m / z calcd for C24H16ClN: 353.0971, found: 353.

Elemental Analysis: C, 82%; H, 5%

Synthetic example  9: Synthesis of intermediate I-9

[Reaction Scheme 9]

Bis (pinacolato) diboron (49 g, 194 mmol) and (1,1'-bis (diphenylphosphine) ferrocene) were dissolved in 1 L of dimethylforamide (DMF) ) dichloropalladium (II) (1.3 g, 1.62 mmol) and potassium acetate (106 g, 405 mmol) were added and heated at 150 ° C for 48 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-9 (64 g, 88%).

HRMS (70 eV, EI +): m / z calcd for C30H28BNO2: 445.2213, found: 445

Elemental Analysis: C, 81%; H, 6%

Synthetic example  10: Synthesis of intermediate I-10

[Reaction Scheme 10]

3-bromobenzaldehyde (127 g, 684 mmol) and sodium hydroxide (41.0 g, 1026 mmol) were added to the solution, and the mixture was stirred at room temperature for 2 hours. Respectively. After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Intermediate I-10 (161 g, 75%) was thus obtained.

HRMS (70 eV, EI +): m / z calcd for C17H13BrO: 312.0150, found: 312.

Elemental Analysis: C, 65%; H, 4%

Synthetic example  11: Synthesis of Intermediate I-11

[Reaction Scheme 11]

3-bromobenzimidamide hydrochloride (95.3 g, 479 mmol) and sodium hydroxide (65.2 g, 1437 mmol) were added to ethanol (1.5 L) in a nitrogen atmosphere. Lt; / RTI > After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Thus, Compound I-11 (91.9 g, 39%) was obtained.

HRMS (70 eV, EI +): m / z calcd for C24H16Br2N2: 489.9680, found: 490.

Elemental Analysis: C, 59%; H, 3%

Synthetic example  12: Synthesis of intermediate I-12

[Reaction Scheme 12]

Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 78.4 g, 173 mmol) was dissolved in 0.8 L of monochlorobenzene (MCB) 345 mmol), and the mixture was refluxed by heating at 130 DEG C for 15 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-12 (57.7 g, 68%).

HRMS (70 eV, EI +): m / z calcd for C24H14Br2N2: 487.9524, found: 488.

Elemental Analysis: C, 59%; H, 3%

Synthetic example  13: Synthesis of intermediate I-13

[Reaction Scheme 13]

After dissolving 4-bromodibenzo [b, d] furan (80 g, 328 mmol) in dimethylformamide (DMF) in a nitrogen atmosphere, bis (pinacolato) diboron (100 g, 393 mmol) bis (diphenylphosphine) ferrocene) dichloropalladium (II) (2.68 g, 3.28 mmol) and potassium acetate (80 g, 820 mmol) were heated at 150 ° C. for 48 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-13 (86 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C18H19BO3: 294.1427, found: 294

Elemental Analysis: C, 74%; H, 7%

Synthetic example  14: Synthesis of Intermediate I-14

[Reaction Scheme 14]

(3-chlorophenyl) boronic acid (57 g, 366 mmol) and tetrakis (triphenylphosphine) palladium (4.2 g, 366 mmol) were dissolved in 1 L of THF in a nitrogen atmosphere, followed by dissolving 4-bromodibenzo g, 3.66 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (126 g, 915 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-14 (93 g, 92%).

HRMS (70 eV, EI +): m / z calcd for C18 H11 ClO: 278.0498, found: 278.

Elemental Analysis: C, 78%; H, 4%

Synthetic example  15: Synthesis of intermediate I-15

[Reaction Scheme 15]

Bis (pinacolato) diboron (100 g, 393 mmol) and (1,1'-bis (diphenylphosphine) ferrocene) were dissolved in 1 L of dimethylformamide (DMF) ) dichloropalladium (II) (2.68 g, 3.28 mmol), and potassium acetate (80 g, 820 mmol) were heated at 150 ° C for 48 hours under reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-15 (112 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C24H23BO3: 370.1740, found: 370

Elemental Analysis: C, 78%; H, 6%

Synthetic example  16: Synthesis of Intermediate I-16

[Reaction Scheme 16]

Intermediate 1-15 (100 g, 277 mmol) was dissolved in 1 L of THF in a nitrogen atmosphere and then 1-bromo-3-chlorobenzene (53 g, 377 mmol) and tetrakis (triphenylphosphine) palladium ) Were added and stirred. Saturated water-saturated potassium carbonate (96 g, 692 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-16 (96 g, 92%).

HRMS (70 eV, EI +): m / z calcd for C24H15ClO: 354.0811, found: 354.

Elemental Analysis: C, 81%; H, 4%

Synthetic example  17: Synthesis of Intermediate I-17

[Reaction Scheme 17]

Bis (pinacolato) diboron (96 g, 378 mmol) and (1,1'-bis (diphenylphosphine) ferrocene) were dissolved in 1 L of dimethylformamide (DMF) ) dichloropalladium (II) (2.57 g, 3.15 mmol) and potassium acetate (77 g, 787 mmol) were added and heated at 150 ° C for 48 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-17 (128 g, 91%).

HRMS (70 eV, EI +): m / z calcd for C30H27BO3: 446.2053, found: 446

Elemental Analysis: C, 81%; H, 6%

Synthetic example  18: Synthesis of Intermediate I-18

[Reaction Scheme 18]

2-naphthaldehyde (107 g, 684 mmol) and sodium hydroxide (41.0 g, 1026 mmol) were added to ethanol (1 L) in a nitrogen atmosphere and stirred at room temperature for 2 hours. Respectively. After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Intermediate I-18 (173 g, 89%) was thus obtained.

HRMS (70 eV, EI +): m / z calcd for C21H6O: 284.1201, found: 284.

Elemental Analysis: C, 89%; H, 6%

Synthetic example  19: Synthesis of intermediate I-19

[Reaction Scheme 19]

4-bromobenzimidamide hydrochloride (141 g, 598 mmol) and sodium hydroxide (71.8 g, 1,794 mmol) were added to 1.5 L of ethanol. Lt; / RTI > After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Intermediate I-19 (114 g, 41%) was thus obtained.

HRMS (70 eV, EI +): m / z calcd for C28H19BrN2: 462.0732, found: 462.

Elemental Analysis: C, 73%; H, 4%

Synthetic example  20: Synthesis of intermediate I-20

[Reaction Scheme 20]

(105 g, 227 mmol) was dissolved in 1 L of monochlorobenzene (MCB) in a nitrogen atmosphere, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 103 g, 453 mmol) was added thereto, and the mixture was refluxed by heating at 130 DEG C for 15 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-20 (68.1 g, 65%).

HRMS (70 eV, EI +): m / z calcd for C28H17BrN2: 460.0575, found: 460.

Elemental Analysis: C, 73%; H, 4%

Synthetic example  21: Synthesis of Intermediate I-21

[Reaction Scheme 21]

The compound 2-bromo-9,9-dimethyl-9H-fluorene (100 g, 366 mmol) was dissolved in 1 L of THF in a nitrogen atmosphere, and then 3-chlorophenyl boronic acid (57 g, 366 mmol) (triphenylphosphine) palladium (4.2 g, 3.66 mmol) was added thereto and stirred. Saturated water-saturated potassuim carbonate (126 g, 915 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-21 (102 g, 92%).

HRMS (70 eV, EI +): m / z calcd for C21H17Cl: 304.1019, found: 304.

Elemental Analysis: C, 83%; H, 6%

Synthetic example  22: Synthesis of Intermediate I-22

[Reaction Scheme 22]

Intermediate I-21 (100 g, 328 mmol) was dissolved in dimethylforamide (DMF) (1 L) under nitrogen atmosphere and bis (pinacolato) diboron (100 g, 393 mmol) and (1,1'- ) dichloropalladium (II) (2.68 g, 3.28 mmol), and potassium acetate (80 g, 820 mmol) were heated at 150 ° C for 48 hours under reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-22 (116 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C27H29BO2: 396.2261, found: 396

Elemental Analysis: C, 82%; H, 7%

Synthetic example  23: Synthesis of Intermediate I-23

[Reaction Scheme 23]

Intermediate 1-22 (110 g, 277 mmol) was dissolved in 1 L of THF in a nitrogen atmosphere and then 1-bromo-3-chlorobenzene (53 g, 377 mmol) and tetrakis (triphenylphosphine) palladium mmol) were added and stirred. Saturated water-saturated potassium carbonate (96 g, 692 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-23 (96 g, 92%).

HRMS (70 eV, EI +): m / z calcd for C27H21Cl: 380.1332, found: 380.

Elemental Analysis: C, 85%; H, 6%

Synthetic example  24: Synthesis of Intermediate I-24

[Reaction Scheme 24]

Bis (pinacolato) diboron (96 g, 378 mmol) and (1,1'-bis (diphenylphosphine) ferrocene) were dissolved in 1 L of dimethylformamide (DMF) ) dichloropalladium (II) (2.57 g, 3.15 mmol) and potassium acetate (77 g, 787 mmol) were added and heated at 150 ° C for 48 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-24 (133 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C33H33BO2: 472.2574, found: 472

Elemental Analysis: C, 84%; H, 7%

Synthetic example  25: Synthesis of intermediate I-25

[Reaction Scheme 25]

The aniline (30 g, 536 mmol) was dissolved in 1 L of tetrahydrofuran (THF) in a nitrogen atmosphere and 2-bromonaphthalene (110 g, 536 mmol) and tris (diphenylideneacetone) dipalladium tris-tert butylphosphine (4.3 g, 21.44 mmol) and sodium tert-butoxide (62 g, 717 mmol) were successively added thereto, followed by heating at 100 ° C for 18 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was purified by flash column chromatography to obtain Intermediate I-25 (110 g, 94%).

HRMS (70 eV, EI +): m / z calcd for C16H13N: 219.1048, found: 219.

Elemental Analysis: C, 88%; H, 6%

Synthetic example  26: Synthesis of Intermediate I-26

[Reaction Scheme 26]

(1,1'-biphenyl) -3-carbaldehyde (125 g, 684 mmol) and sodium hydroxide (41.0 g, 1026 mmol) were dissolved in ethanol (1 L) ) And the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Intermediate I-26 (180 g, 89%) was thus obtained.

HRMS (70 eV, EI +): m / z calcd for C23H18O: 310.1358, found: 310.

Elemental Analysis: C, 89%; H, 6%

Synthetic example  27: Synthesis of Intermediate I-27

[Reaction Scheme 27]

4-bromobenzimidamide hydrochloride (141 g, 598 mmol) and sodium hydroxide (71.8 g, 1,794 mmol) were added to 1.5 L of ethanol in a nitrogen atmosphere. Lt; / RTI > After completion of the reaction, the reaction solution was filtered and washed with a small amount of ethanol. Intermediate I-27 (119 g, 41%) was thus obtained.

HRMS (70 eV, EI +): m / z calcd for C30H21BrN2: 488.0888, found: 488.

Elemental Analysis: C, 74%; H, 4%

Synthetic example  28: Synthesis of intermediate I-28

[Reaction Scheme 28]

(135 g, 227 mmol) was dissolved in 1 L of monochlorobenzene (MCB) in a nitrogen atmosphere, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 103 g, 453 mmol) was added thereto, and the mixture was refluxed by heating at 130 DEG C for 15 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was purified by flash column chromatography to obtain Intermediate I-28 (73 g, 67%).

HRMS (70 eV, EI +): m / z calcd for C30H19BrN2: 486.0732, found: 486.

Elemental Analysis: C, 74%; H, 4%

Synthetic example  29: Synthesis of Intermediate I-29

[Reaction Scheme 29]

3-bromo-9-phenyl-9H-carbazole (115 g, 366 mmol) was dissolved in 1 L of THF in a nitrogen atmosphere. Then, 3-chlorophenyl boronic acid (57 g, 366 mmol) and tetrakis (triphenylphosphine) palladium (4.2 g, 3.66 mmol) were added thereto and stirred. Saturated water-saturated potassuim carbonate (126 g, 915 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-29 (118 g, 92%).

HRMS (70 eV, EI +): m / z calcd for C24H16ClN: 353.0971, found: 353.

Elemental Analysis: C, 81%; H, 5%

Synthetic example  30: Synthesis of Intermediate I-30

[Reaction Scheme 30]

Bis (pinacolato) diboron (100 g, 393 mmol) and (1,1'-bis (diphenylphosphine) ferrocene) were dissolved in 1 L of dimethylforamide (DMF) ) dichloropalladium (II) (2.68 g, 3.28 mmol) and potassium acetate (80 g, 820 mmol) were added and heated at 150 ° C for 48 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-30 (131 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C30H28BNO2: 445.2213, found: 445

Elemental Analysis: C, 81%; H, 6%

Synthetic example  31: Synthesis of Intermediate I-31

[Reaction Scheme 31]

Intermediate 1-30 (110 g, 269 mmol) was dissolved in 1 L of THF in a nitrogen atmosphere and then 1-bromo-3-chlorobenzene (62 g, 322 mmol) and tetrakis (triphenylphosphine) palladium mmol) were added and stirred. Saturated water-saturated potassium carbonate (93 g, 672 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain the above compound I-31 (99 g, 89%).

HRMS (70 eV, EI +): m / z calcd for C30 H20 ClN: 429.1284, found: 429.

Elemental Analysis: C, 84%; H, 5%

Synthetic example  32: Synthesis of Intermediate I-32

[Reaction Scheme 32]

Intermediate I-31 (95 g, 221 mmol) was dissolved in dimethylforamide (DMF) (1 L) in a nitrogen atmosphere and bis (pinacolato) diboron (67 g, 265 mmol) and (1,1'- ) dichloropalladium (II) (1.8 g, 2.21 mmol) and potassium acetate (54 g, 552 mmol) were added and the mixture was refluxed by heating at 150 ° C for 48 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain Intermediate I-32 (98 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C36H32BNO2: 521.2526, found: 521

Elemental Analysis: C, 83%; H, 6%

Synthesis of final compound

Synthetic example  33: Synthesis of compound 1

[Reaction Scheme 33]

In a nitrogen atmosphere, 9H-carbazole (5.4 g, 32.6 mmol) and tris (diphenylideneacetone) dipalladium (o) (0.163 g, 0.163 mmol) were dissolved in 0.18 L of toluene, , tris-tert butylphosphine (0.26 g, 0.652 mmol) and sodium tert-butoxide (1.9 g, 20 mmol) were successively added thereto, and the mixture was refluxed by heating at 100 ° C for 18 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 1 (8 g, 77%).

HRMS (70 eV, EI +): m / z calcd for C48H30N4: 662.2470, found: 662.

Elemental Analysis: C, 87%; H, 5%

Synthetic example  34: Synthesis of Compound 3

[Reaction Scheme 34]

Intermediate I-9 (11 g, 24.3 mmol) and tetrakis (triphenylphosphine) palladium (0.28 g, 0.243 mmol) were dissolved in 1 L of THF in a nitrogen atmosphere, And stirred. Saturated water-saturated potassuim carbonate (8 g, 60 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 3 (13 g, 83%).

HRMS (70 eV, EI +): m / z calcd for C48 H31 N3: 649.2518, found: 649.

Elemental Analysis: C, 89%; H, 5%

Synthetic example  35: Synthesis of Compound 10

[Reaction Scheme 35]

(10 g, 24.3 mmol) was dissolved in 0.18 L of toluene in a nitrogen atmosphere and then 9H-carbazole (8 g, 48.6 mmol) and tris (diphenylideneacetone) dipalladium (0) (0.163 g, , tris-tert butylphosphine (0.19 g, 0.243 mmol) and sodium tert-butoxide (2.8 g, 29 mmol) were successively added, and the mixture was refluxed by heating at 100 ° C for 18 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 10 (13 g, 79%).

HRMS (70 eV, EI +): m / z calcd for C48H30N4: 662.2470, found: 662.

Elemental Analysis: C, 87%; H, 5%

Synthetic example  36: Synthesis of Compound 13

[Reaction Scheme 36]

Intermediate I-13 (10 g, 32.6 mmol) and tris (diphenylideneacetone) dipalladium (o) (0.163 g, 0.163 mmol) were dissolved in 0.18 L of toluene in a nitrogen atmosphere, ), tris-tert butylphosphine (0.26 g, 0.652 mmol) and sodium tert-butoxide (1.9 g, 20 mmol) were successively added thereto, followed by heating at 100 ° C for 18 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 13 (8.5 g, 78%).

HRMS (70 eV, EI +): m / z calcd for C48H28N2O2: 664.2151, found: 664.

Elemental Analysis: C, 87%; H, 4%

Synthetic example  37: Synthesis of compound 15

[Reaction Scheme 37]

Intermediate I-17 (11 g, 24.3 mmol) and tetrakis (triphenylphosphine) palladium (0.28 g, 0.243 mmol) were dissolved in 1 L of THF in a nitrogen atmosphere, And stirred. Saturated water-saturated potassuim carbonate (8 g, 60 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain the compound 15 (13 g, 83%).

HRMS (70 eV, EI +): m / z calcd for C48H30N2O: 650.2358, found: 650.

Elemental Analysis: C, 87%; H, 5%

Synthetic example  38: Synthesis of Compound 41

[Reaction Scheme 38]

Intermediate I-24 (12 g, 24.3 mmol) and tetrakis (triphenylphosphine) palladium (0.28 g, 0.243 mmol) were dissolved in 1 L of THF in a nitrogen atmosphere, And stirred. Saturated water-saturated potassuim carbonate (8 g, 60 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain the above compound 41 (14 g, 79%).

HRMS (70 eV, EI +): m / z calcd for C55H38N2: 726.3035, found: 726.

Elemental Analysis: C, 91%; H, 5%

Synthetic example  39: Synthesis of Compound 49

[Reaction Scheme 39]

Intermediate I-25 (4 g, 16.3 mmol) and tris (diphenylideneacetone) dipalladium (o) (0.163 g, 0.163 mmol) were dissolved in 0.18 L of toluene in a nitrogen atmosphere, ), tris-tert butylphosphine (0.26 g, 0.652 mmol), and sodium tert-butoxide (1.9 g, 20 mmol) were successively added and refluxed by heating at 100 ° C for 18 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 49 (9 g, 85%).

HRMS (70 eV, EI +): m / z Calcd for C46 H31 N3: 625.2518, found: 625.

Elemental Analysis: C, 88%; H, 5%

Synthetic example  40: Synthesis of Compound 97

[Reaction Scheme 40]

Intermediate I-32 (13 g, 24.3 mmol) and tetrakis (triphenylphosphine) palladium (0.28 g, 0.243 mmol) were dissolved in 1 L of THF in a nitrogen atmosphere, And stirred. Saturated water-saturated potassuim carbonate (8 g, 60 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain the compound 97 (15 g, 85%).

HRMS (70 eV, EI +): m / z Calcd for C54 H35 N3: 725.2831, found: 725.

Elemental Analysis: C, 89%; H, 5%

Fabrication of organic light emitting device

Example  One

An organic light emitting device was prepared by using Compound 1 obtained in Synthesis Example 33 as a host and using acetylacetonatobis (2-phenylquinolinato) iridium (Ir (pq) 2acac) as a dopant.

As the anode, ITO was used to a thickness of 1500 Å, and aluminum (Al) was used as a cathode to a thickness of 1000 Å. Specifically, an explanation will be given of a method of manufacturing an organic light emitting device. An ITO glass substrate having a sheet resistance of 15 Ω / cm 2 is cut into a size of 50 mm × 50 mm × 0.7 mm, and is cut in acetone, isopropyl alcohol and pure water After ultrasonic cleaning for 15 minutes, UV ozone cleaning was used for 30 minutes.

The degree of vacuum in the upper substrate 650 × 10 ^-7 Pa, the deposition rate of 0.1 to 0.3 nm / s in terms 4,4'-bis [N- [4- { N, N-bis (3-methylphenyl) amino} -phenyl ] -N-phenylamino] biphenyl [DNTPD] was vacuum-deposited to form a hole injection layer having a thickness of 600 Å. Subsequently, HT-1 was vacuum vapor deposited under the same vacuum deposition conditions to form a 300 Å thick hole transport layer. Next, a light emitting layer having a thickness of 300 angstroms was formed using the compound 1 obtained in Synthesis Example 33 under the same vacuum deposition conditions. At this time, acetylacetonatobis (2-phenylquinolinato) iridium (Ir (pq) 2acac) Respectively. At this time, the deposition rate of the phosphorescent dopant was adjusted so that the phosphorescent dopant content was 7% by weight when the total amount of the light emitting layer was 100% by weight.

Bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum (BAlq) was deposited on the light emitting layer using the same vacuum deposition conditions to form a hole blocking layer having a thickness of 50 Å. Subsequently, Tris (8-hydroxyquinolinato) aluminum (Alq3) was deposited under the same vacuum deposition conditions to form an electron transport layer having a thickness of 250 ANGSTROM. LiF and Al were sequentially deposited on the electron transport layer as cathodes to fabricate an organic photoelectric device.

 The structure of the organic photoelectric device was ITO / DNTPD (60 nm) / HT-1 (30 nm) / EML (compound 1 (93 wt%) + Ir (pq) 2acac (7 wt%), 5 nm) / Alq3 (25 nm) / LiF (1 nm) / Al (100 nm).

Example  2

An organic luminescent device was prepared in the same manner as in Example 1 except that the compound 3 obtained in Synthesis Example 34 was used instead of the compound 1 obtained in Synthesis Example 33. [

Example  3

An organic luminescent device was prepared in the same manner as in Example 1, except that the compound 10 obtained in Synthesis Example 35 was used instead of the compound 1 obtained in Synthesis Example 33.

Example  4

An organic luminescent device was produced in the same manner as in Example 1 except that the compound 13 obtained in Synthesis Example 36 was used instead of the compound 1 obtained in Synthesis Example 33. [

Example  5

An organic luminescent device was prepared in the same manner as in Example 1 except that the compound 15 obtained in Synthesis Example 37 was used instead of the compound 1 obtained in Synthesis Example 33. [

Example  6

An organic luminescent device was prepared in the same manner as in Example 1 except that the compound 41 obtained in Synthesis Example 38 was used instead of the compound 1 obtained in Synthesis Example 33. [

Example  7

An organic luminescent device was prepared in the same manner as in Example 1 except that the compound 49 obtained in Synthesis Example 39 was used instead of the compound 1 obtained in Synthesis Example 33. [

Example  8

An organic luminescent device was prepared in the same manner as in Example 1 except that the compound 97 obtained in Synthesis Example 40 was used instead of the compound 1 obtained in Synthesis Example 31. [

Comparative Example  One

An organic light emitting device was prepared in the same manner as in Example 1 except that 4,4'-di (9H-carbazol-9-yl) biphenyl (CBP) was used instead of the compound 1 obtained in Synthesis Example 31.

The structures of DNTPD, BAlq, HT-1, CBP and Ir (pq) 2acac used in the production of the organic light emitting device are as follows.

evaluation

The current density change, the luminance change, and the light emitting efficiency of the organic light emitting device according to Examples 1 to 8 and Comparative Example 1 were measured according to the voltage.

The specific measurement method is as follows, and the results are shown in Table 1.

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light-emitting device manufactured, luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) at the same current density (10 mA / cm 2) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

(4) Life measurement

The initial luminance (cd / m2) was emitted at 3000 cd / m < ² > and the decrease in luminance over time was measured.

No. compound The driving voltage (V) color
(EL color) efficiency
(cd / A) 90% lifetime (h)
At 3000 cd / m ² Example 1 Compound 1 7.0 Red 48.1 74 Example 2 Compound 3 6.6 Red 43.5 110 Example 3 Compound 10 7.1 Red 47.5 71 Example 4 Compound 13 6.7 Red 44.1 75 Example 5 Compound 15 7.0 Red 47.9 60 Example 6 Compound 41 6.6 Red 48.6 84 Example 7 Compound 49 7.2 Red 46.2 72 Example 8 Compound 97 7.1 Red 48.0 76 Comparative Example 1 CBP 7.4 Red 37.2 50

Referring to Table 1, it can be seen that the organic light emitting devices according to Examples 1 to 8 have significantly improved luminous efficiency and lifetime characteristics as compared with the organic light emitting device according to Comparative Example 1. [

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100, 200: Organic light emitting device
105: organic layer
110: cathode
120: anode
130: light emitting layer
140: hole assist layer

Claims (13)

An organic compound represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
Two of X are N, two are C,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,
R ⁵ to R ¹² each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,
L ¹ to L ⁶ each independently represent a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group or a substituted or unsubstituted quaterphenylene group,
n ¹ to n ⁴ each independently represents an integer of 0 to 5,
the sum of n ¹ to n ⁴ is an integer of 2 or more,
Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group, a group represented by the following formula A, a group represented by the following formula (B)
At least one of Ar ¹ and Ar ² is a group represented by the following formula (A), a group represented by the following formula (B)
(A)

In the above formula (A)
Y is O, S, CR ^a R ^b , SiR ^c R ^d or NR ^e ,
R ¹³ to R ²⁰ and R ^a to R ^e each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocycle A combination thereof, or a linking point with L ⁵ or L ⁶ in the above formula (1)
R ¹³ to R ²⁰ are each independently present or two adjacent ones are connected to each other to form a fused ring,
[Chemical Formula B]

In the above formula (B)
R ²¹ to R ³⁰ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,
R ²¹ to R ³⁰ are each independently present or two adjacent ones are connected to form a fused ring,
Wherein the at least one hydrogen is selected from the group consisting of deuterium, a C1 to C30 amine group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, C30 heterocycle, a fluoro group, a C1 to C10 trifluoroalkyl group or a cyano group,
* Is the point of connection with L ⁵ or L ⁶ in formula (1).

The method of claim 1,
An organic compound represented by the following formula (2) or (3):
(2)

(3)

In the general formula (2) or (3)
R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,
R ⁵ to R ¹² each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,
L ¹ to L ⁶ each independently represent a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group or a substituted or unsubstituted quaterphenylene group,
n ¹ to n ⁴ each independently represents an integer of 0 to 5,
the sum of n ¹ to n ⁴ is an integer of 2 or more,
Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group, a group represented by the formula A, a group represented by the formula B, or a combination thereof,
At least one of Ar ¹ and Ar ² is a group represented by the above formula (A), a group represented by the above formula (B)
Wherein the at least one hydrogen is selected from the group consisting of deuterium, a C1 to C30 amine group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, C30 heterocycle, a fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group.
3. The method of claim 2,
An organic compound represented by the following formula (2A) or (3A):
(2A)

[Chemical Formula 3]

In the above formula (2A) or (3A)
R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,
R ⁵ to R ⁸ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,
L ¹ to L ⁴ each independently represent a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group or a substituted or unsubstituted quaterphenylene group,
n ¹ and n ² are each independently an integer of 0 to 5,
the sum of n ¹ and n ² is an integer of 2 or more,
Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group, a group represented by the formula A, a group represented by the formula B, or a combination thereof,
At least one of Ar ¹ and Ar ² is a group represented by the above formula (A), a group represented by the above formula (B)
Wherein the at least one hydrogen is selected from the group consisting of deuterium, a C1 to C30 amine group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, C30 heterocycle, a fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group.
The method of claim 1,
Wherein n ¹ and n ² in Formula 1 are each independently 1 to 5.
The method of claim 1,
Wherein R < ³ > and R < ⁴ > in the above formula (1) are each independently hydrogen.
The method of claim 1,
L ¹ to L ⁶ in Formula 1 are each independently a single bond or an organic compound that is one of the groups listed in Group 1 below:
[Group 1]

In the group 1,
R ³¹ to R ³⁴ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,
Wherein the at least one hydrogen is selected from the group consisting of deuterium, a C1 to C30 amine group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, C30 heterocycle, a fluoro group, a C1 to C10 trifluoroalkyl group or a cyano group,
* Is the connection point.
The method of claim 6,
Wherein each of R ³¹ to R ³⁴ is independently hydrogen.
The method of claim 1,
Wherein the formula (A) is one of the groups listed in the following group 2:
[Group 2]

In the group 2,
R ³⁵ to R ³⁹ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,
Wherein the at least one hydrogen is selected from the group consisting of deuterium, a C1 to C30 amine group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, C30 heterocycle, a fluoro group, a C1 to C10 trifluoroalkyl group or a cyano group,
* Is the connection point.
The method of claim 1,
Wherein the formula (B) is one of the groups listed in group 3 below:
[Group 3]

In the group 3,
R ⁴⁰ to R ⁴⁷ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or combinations thereof ,
Wherein the at least one hydrogen is selected from the group consisting of deuterium, a C1 to C30 amine group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, C30 heterocycle, a fluoro group, a C1 to C10 trifluoroalkyl group or a cyano group,
* Is the connection point.
The method of claim 1,
Organic compounds listed in Group 4 below:
[Group 4]

Positive and negative facing each other, and
At least one organic layer positioned between the anode and the cathode,
/ RTI >
Wherein the organic layer comprises the organic compound according to any one of claims 1 to 10.
12. The method of claim 11,
Wherein the organic layer includes a light emitting layer,
Wherein the light emitting layer comprises the organic compound.
12. A display device comprising the organic electroluminescent device according to claim 11.

Images